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“It was not simply out of a spirit of contradiction that I exposed a light source to a magnetic field,” so said Pieter Zeeman, on receiving the 1902 Nobel Prize in Physics with Hendrik Lorentz. The effect of a magnetic field on light had been studied years before, most notably by Michael Faraday: in 1845, he showed that when light passes through certain materials immersed in a magnetic field, the plane in which the light oscillates is rotated — now known as Faraday rotation, this was the first experimental evidence of a connection between light and electromagnetism. Later in his life, Faraday wondered whether a magnetic field could have a direct influence on a light source — specifically, on the light emitted by atoms or molecules when excited in a flame. This investigation was the last experiment recorded in his laboratory notebook, but the result was negative: on 12 March 1862, Faraday wrote that there was “not the slightest effect demonstrable”. Possibly referring to this experiment, James Clerk Maxwell stated in 1870, on the subject of light-emitting particles, that “no force in nature can alter even very slightly either their mass or their period of oscillation”. This statement, “coming from the mouth of the founder of the electromagnetic light theory and spoken with such intensity”, greatly troubled Zeeman. Motivated by his own studies of the magneto-optic Kerr effect (a phenomenon closely related to the Faraday effect, but measured for light reflected from a magnetized medium), Zeeman decided in 1896 to revisit Faraday’s last experiment. Two recent technical advances proved useful. The first was the invention, by Henry Augustus Rowland, of diffraction gratings consisting of mirrors ruled with a large number of parallel lines; Rowland’s gratings offered unprecedented spectral resolution. The second was the steady development of photography, which brought with it the possibility of capturing spectra and analysing them later. Zeeman was soon able to show that, for a sodium flame placed in an electromagnet, there was a broadening of the sodium D-lines when the magnet was switched on. The effect was reportedly far from conspicuous; however, firm support was provided by the observation of characteristic polarization effects. This confirmed predictions made by Lorentz — immediately after seeing the first results produced by Zeeman, he had proposed a model of electrons vibrating within the light- emitting particles. In 1897, Zeeman reported much clearer splittings in the blue line of cadmium. Although Lorentz’s theory did explain the most elementary splitting patterns, it was not long before numerous exceptions were found, as more elements were studied in greater detail. “Nature gives us all, including Professor Lorentz, surprises”, concluded Zeeman. He might have been surprised to know that it would take nearly three decades for this ‘anomalous Zeeman effect’ to be explained fully — when it was realized that the splitting is a consequence of spin (Milestone 3). Andreas Trabesinger, Senior Editor, Nature Physics ORIGINAL RESEARCH PAPERS Zeeman, P. Over den invloed eener magnetisatie op den aard van het door een stof uitgezonden licht. Versl. Kon. Akad. Wetensch. Amsterdam 5, 181–184, 242–248 (1896) | Zeeman, P. Over doubletten en tripletten in het spektrum, teweeggebracht door uitwendige magnetische krachten. Versl. Kon. Akad. Wetensch. Amsterdam 6, 13–18, 99–102, 260–262 (1897) fuRtHER REAdING Zeeman, P. The effect of magnetisation on the nature of light emitted by a substance. Nature 55, 347 (1897) | Zeeman, P. Light radiation in a magnetic field, Nobel Lecture, 2 May, 1903. Nobelprize.org [online], <http://nobelprize.org/nobel_prizes/physics/laureates/1902/ zeeman-lecture.html> (1903) | Rayleigh. Pieter Zeeman. 1865–1943. Obit. Not. Fellows R. Soc. 4, 591–595 (1944) m I L E S tO N E 1 Physics is set spinning Razvanj p | D re am st im e. co m …it would take nearly three decades for this ‘anomalous Zeeman effect’ to be explained… Nature MILeStONeS | Spin March 2008 | S5 MILESTONES © 2008 Nature Publishing Group http://nobelprize.org/nobel_prizes/physics/laureates/1902/zeeman-lecture.html http://nobelprize.org/nobel_prizes/physics/laureates/1902/zeeman-lecture.html the fact that quantities such as energy, mass and charge come in discrete and indivisible amounts, or quanta, is now so fundamental to our understanding of the universe that it is often taken for granted. It is difficult to appreciate fully just how counterintuitive an idea it was to suggest that the angular momentum of an object should take on similarly quantized values. the roots of this idea lay in the 1913 description by Niels Bohr of the structure of the atom, later refined by arnold Sommerfeld in 1916, which suggested that not only do electrons exist in orbitals of well-defined size and shape, but that the orientation of these orbitals is strictly defined — a characteristic known as space quantization. In 1920, most physicists, including Max Born, who was one of the architects of quantum mechanics, considered the idea to be more a mathematical abstraction than a concrete physical reality. Yet, in 1922, Otto Stern and Walter Gerlach demonstrated such a reality beyond all reasonable doubt. their experiment involved passing a collimated beam of silver atoms through an inhomogeneous magnetic field and onto a glass slide where the deposits formed a pattern. classical models suggested that the electron orbitals around the nucleus of these atoms should be randomly and continuously distributed, and that a single, broad and continuous spot of silver should form in the centre of the slide. the Bohr–Sommerfeld model, by contrast, predicted that space quantization of these orbitals should cause the beam to be split into several discrete parts in the inhomogeneous field, forming discrete lines of silver deposits on the slide. Despite its elegant simplicity, the experiment almost never happened. For one thing, for there to be any observable splitting, the alignment of the beam and the centre of the magnetic field had to be just right. More prosaically, in the middle of a worsening economic depression, funding the construction of the experiment proved to be almost as difficult. thankfully, perseverance on the part of Stern and Gerlach, and a cheque for several hundred dollars provided by henry Goldman (co-founder of the investment firm Goldman Sachs), allowed them to observe the splitting predicted by quantum theory — a result m I L E S tO N E 2 Answers on a postcard By 1920, physicists were still struggling to make sense of the splitting of atomic spectral lines in a magnetic field, discovered by Pieter Zeeman (Milestone 1). With the Bohr atom of 1913 had come the notion of quantized orbits for electrons around the atomic nucleus. Perhaps, it was thought, the Zeeman splitting arose from the interaction between the angular momenta of the ‘core’ of electrons in closed shells and of the ‘radiant electron’ in the outermost unclosed shell. Yet calculations made on this basis — notably by Arnold Sommerfeld and Alfred Landé, using an Ersatzmodell — failed to match experimental data. The helium atom posed a particular problem: which of its two electrons should be considered ‘core’ and which ‘radiant’? Also, no one could explain why, if an atom were in its ground state, all its electrons were not bound into the innermost shell. In 1924, Landé gave up the struggle as “impossible once and for all”. Wolfgang Pauli, however, was undeterred. He dropped the notion of an interaction between core and radiant electron and proposed instead that line splitting arose as a consequence of an intrinsic property of the electron: “eine klassisch nicht beschreibbare Art von Zweideutigkeit” — a classically indescribable two- valuedness — as he wrote in the first of his two 1925 Zeitschrift fürPhysik papers. m I L E S tO N E 3 The spinning electron Ralph Kronig, a young physicist in Landé’s laboratory, suggested to Pauli that this might be imagined as the rotation of an electron about its own axis with one half-unit of angular momentum — in other words, spin. Pauli disliked the idea: it was still ‘classically indescribable’ and, moreover, the calculations of level splitting by Kronig were a factor of two out from measured values. Kronig did not publish, but later that year George Uhlenbeck and Samuel Goudsmit did — the same idea, beset by the same problems. Pauli still didn’t like it. Nevertheless, it was a short step from the ‘two-valuedness’ of an intrinsic electron quantum number for Pauli to realize why all electrons in an atom are not bound in the innermost state. Guided by comments made by Edmund C. Stoner, Pauli saw that, if the four numbers used to describe line splitting (denoted n, k, m and j) were thought of as quantum numbers of the electron, then once an electron existed in some state defined by particular values of n, k, m and j, no other electron could enter that state. Using this ‘exclusion principle’, Pauli could derive the exact shell structure of the atom — two electrons to close the innermost shell, eight to close the next, and so on. The deal was sealed early in 1926, with the publication by Llewellyn H. Thomas of what became known as the Pauli and Bohr watch a spinning top. Photograph by Erik Gustafson, courtesy of AIP Emilio Segrè Visual Archives, Margrethe Bohr Collection. Postcard from Gerlach to Bohr. Image courtesy of Niels Bohr Archive, Copenhagen. Milestones S6 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group The idea of the spinning electron, as proposed by Samuel Goudsmit and George Uhlenbeck in 1925 (Milestone 3), and incorporated into the formalism of quantum mechanics by Wolfgang Pauli, was a solution of expediency. Yet this contrivance threw up a more fundamental question: as a 25-year-old postdoctoral fellow at the University of Cambridge formulated the problem in 1928, why should nature have chosen this particular model for the electron, instead of being satisfied with a point charge? The young postdoc’s name was Paul Dirac, and in two papers published in the Proceedings of the Royal Society of London, he set out to explain why. Using the clear, austere prose and adroit mathematics that were his hallmarks, he showed how spin emerged as a natural consequence of the correct application of special relativity to the quantum mechanics of the electron. Dirac was able to remove the nonlinearities in space and time derivatives that had confounded other attempts to marry those two great new physical theories. The corollary of his logic was that the wavefunction of the electron must have four components, and must be operated on by four-dimensional matrices. These matrices required an additional degree of freedom beyond position and momentum in the physical description of the electron. Inspection revealed them to be extensions of the two-dimensional spin matrices introduced by Pauli in his earlier ad hoc treatment. Applied to an electron in an electromagnetic field, the new formalism delivered the exact value of the magnetic moment assumed in the spinning electron model. What had emerged was an equation that, in its author’s words, “governs most of physics and the whole of chemistry”. Dirac was a famously modest man, and was not wont to exaggerate. The Dirac equation is still today the best description not just of the electron, but of all spin-1/2 particles — including all the quarks and leptons from which matter is made. When asked what had led him to his formula, Dirac replied simply “I found it beautiful”. His equation is indeed a powerful example of the deep and mysterious connection between the language of mathematics and the expressions of the physical world. Yet, however much beauty might be indicative of rightness, a physical theory is judged on its predictive power. The Dirac equation did not disappoint. The interpretation of two of its four solutions was clear: they were the two spin states of the electron. But the other two solutions seemed to require particles exactly like electrons, but with a positive charge. Dirac did not immediately and explicitly state the now-obvious conclusion — out of “pure cowardice”, he explained later. But when, in 1932, Carl Anderson confirmed the existence of the positron, Dirac’s fame was assured. He shared the 1933 Nobel Prize in Physics — its second-youngest-ever recipient — and his equation went on to become the bedrock of quantum electrodynamics, the quantum field theory of the electromagnetic interaction. Following his death in 1984, a stone was set into the floor of Westminster Abbey in London. It was inscribed with his name and iγ · дΨ = mΨ — the shortest and sweetest rendering of his extraordinary brainchild. Richard Webb, Senior Editor, Nature News & Views ORIGINAL RESEARCH PAPERS Dirac, P. A. M. The quantum theory of the electron. Proc. R. Soc. Lond. A 117, 610–624 (1928); ibid. 118, 351–361 (1928) fuRtHER REAdING Dirac, P. A. M. The Principles of Quantum Mechanics (Int. Ser. Monograph. Phys. 27) 4th edn (Oxford Univ. Press, Oxford, UK, 1982) | Pais, A., Jacob, M., Olive, D. I. & Atiyah, M. F. Paul Dirac: The Man and his Work (Cambridge Univ. Press, Cambridge, UK, 1998) m I L E S tO N E 4 A relative success that is now most famously recorded on a postcard from Gerlach to Bohr congratulating him on the success of his theory. although the Stern–Gerlach experiment categorically disproved classical models of the atom, it was also inconsist- ent with the Bohr–Sommerfeld model. In fact, the observed splitting of the silver beam had nothing to do with the orbital angular momentum, but was due to the spin angular momen- tum of the unpaired electron in the atomic structure of silver — something that was not appreciated until years later, follow- ing the introduction of the idea of electron spin by Wolfgang Pauli (Milestone 3). Not content with realizing what is perhaps the clearest and most direct demonstration of the quantum nature of atoms, Stern went on to demonstrate and measure the quantized spin of the proton — together with the size of its magnetic moment — for which he was awarded the 1943 Nobel Prize in Physics. Ed Gerstner, Senior Editor, Nature Physics ORIGINAL RESEARCH PAPERS Gerlach, W. & Stern, O. Der experimentelle Nachweis der Richtungsquantelung im Magnetfeld. Z. Phys. 9, 349–352 (1922) | Frisch, R. & Stern, O. Über die magnetische Ablenkung von Wasserstoff-Molekülen und das magnetische Moment des Protons. I. Z. Phys. 85, 4–16 (1933) | Estermann, I. & Stern, O. Über die magnetische Ablenkung von Wasserstoff-Molekülen und das magnetische Moment des Protons. II. Z. Phys. 85, 17–24 (1933) fuRtHER REAdING Friedrich, B. & Herschbach, D. Stern and Gerlach: how a bad cigar helped reorient atomic physics. Phys. Today 56 (12), 53–59 (2003) Pauli’s ‘two- valuedness’ was indeed due to the spin of the electron. ‘Thomas factor’ — the missing factor of two. Thomas’ classical analysis finally won over Pauli the perfectionist (Paul Dirac would soon supply the full quantum relativistic formalism; Milestone 4). Pauli’s ‘two-valuedness’ was indeed due to the spin of the electron. Probably the great man was cheered, having written to Kronig in May 1925, “At the moment physics is again terribly confused. In any case, it is too difficult for me, and I wish I had been a movie comedian or something of the sort and had never heard of physics.” Alison Wright, Chief Editor, Nature Physics ORIGINAL RESEARCH PAPERS Stoner, E. C. The distribution of electrons among atomic levels. Phil. Mag. 48, 719–736 (1924) | Pauli, W. Über den Einfluß der Geschwindigkeitsabhängigkeit der Elektronenmasse auf den Zeemaneffekt. Z. Phys. 31, 373–385 (1925)| Pauli, W. Über den Zusammenhang des Abschlusses der Elektronengruppen im Atom mit der Komplexstruktur der Spektren. Z. Phys. 31, 765–783 (1925) | Uhlenbeck, G. E. & Goudsmit, S. A. Ersetzung der Hypothese vom unmechanischen Zwang durch eine Forderung bezüglich des inneren Verhaltens jedes einzelnen Elektrons. Naturwiss. 13, 953–954 (1925) | Thomas, L. H. The motion of the spinning electron. Nature 117, 514 (1926) fuRtHER REAdING Pauli, W. Exclusion principle and quantum mechanics, Nobel Lecture, 13 December, 1946. Nobelprize.org [online], <http://nobelprize.org/nobel_prizes/ physics/laureates/1945/pauli-lecture.html> (1946) | Tomonaga, S. The Story of Spin (Univ. Chicago Press, Chicago, 1997) Im ag e co ur te sy o f L id a Lo pe s C ar do zo K in de rs le y. Nature MILeStONeS | Spin March 2008 | S7 © 2008 Nature Publishing Group Since the earliest observation that a lump of lodestone attracts iron, around 600 Bc, magnetism has attracted numerous philosophers and physicists eager to understand its secrets. Yet the physical explana- tion came only with the development of quantum mechanics in the 1920s — after all, magnetism is a purely quantum effect arising from the ‘spin’ property of the electron. By convention, we say that the spin points either up or down. this means that there are two distinct spin states instead of one; hence, certain theories were out by a factor of two with respect to experiments. Following a series of papers published in the years 1925 to 1927 — during which quantum mechan- ics was developed, interpreted and applied to atoms with more than one electron outside a closed shell — Werner heisenberg solved the mystery of ferromagnetism using the concept of spin plus the exclusion principle formulated by Wolfgang Pauli, which states that two electrons with the same energy and momentum cannot occupy the same quantum state. In other words, two electrons with the same energy but different spins can lie in the same orbital. the m I L E S tO N E 5 An attractive theory In 1932, Werner Heisenberg mused on an odd fact. The proton and the neutron (which had been discovered only earlier that same year by James Chadwick) had almost exactly the same mass. Despite their different charges, they also responded identically to the forces that dominate within the atomic nucleus. To Heisenberg’s nose, this had a whiff of an uncovered symmetry about it. Appropriating the mathematics that Wolfgang Pauli had used to describe spin (Milestone 3), he postulated that the proton and neutron were two states of the same particle, the nucleon. These states differed only in a quantity analogous to spin — the ‘isotopic spin’, or isospin as it came to be known. The nuclear force conserved isospin, which accounted for the similarities between protons and neutrons. Other forces, such as electromagnetism, broke isospin symmetry, which explained the nucleons’ differences. As Eugene Wigner wrote of the isospin concept in a 1937 paper, “no such states are known to be of any importance […] [but they] will turn out to be very useful”. In that paper, he used isospin to predict correctly the energies of all nuclei up to atomic number 42; more recent work has extended that success to even heavier nuclei. Much like the quantum-relativistic prediction of a spinning electron by Paul Dirac (Milestone 4), isospin was an example of what Wigner would later, in a celebrated essay, describe as the “unreasonable effectiveness” of mathematics in predicting physical phenomena. And how. In 1935, Hideki Yukawa modelled a nuclear force mediated by lighter particles exchanged between the nucleons. Isospin conservation demanded three such particles. Believers in unreasonable effectiveness could not have been surprised when, some 10 years later, three particles answering the description turned up in cosmic rays and in the first accelerator experiments: the two charged and one neutral pion. In 1954, Chen Ning Yang and Robert Mills took the ideas of Yukawa further to establish their principle of ‘gauge invariance’. This was the centrepiece of m I L E S tO N E 6 Spin’s nuclear sibling a generalized mathematical description of forces mediated by exchange particles of integer spin and isospin — the bedrock of current quantum field theories of the fundamental forces of nature. Meanwhile, however, physics was entering the accelerator age, and the discovery of a seemingly unordered menagerie of particles similar to the pions was straining the foundation of isospin symmetry. It gradually became clear that isospin was not a fundamental symmetry, but just one corner of a larger edifice. In addition, the proton and neutron were not two states of the same particle. In fact, they were not elementary particles at all, but were made up of smaller entities — quarks. facts that an electron has spin, as well as charge, and that two identical electrons must occupy different states, are the keys to the periodic table. until then, the force aligning the electron spins could not be explained in terms of known interactions, none of which was strong enough. In the words of Paul Dirac: “the solution of this difficulty […] is provided by the exchange (austausch) interaction of the electrons, which arises owing to the electrons being indistinguishable one from another. two electrons may change places without our knowing it, and the proper allowance for the possibility of quantum jumps of this nature, which can be made in a treat- ment of the problem by quantum mechanics, gives rise to the new kind of interaction. the energies involved, the so-called exchange energies, are quite large.” By applying such an energy tax on indistinguishable particles, ST O C KB YT E Werner Heisenberg. Photograph by Friedrich Hund, courtesy of AIP Emilio Segrè Visual Archives. Milestones S8 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group Once deprived of its original legitimacy, one might have expected spin’s nuclear sibling to disappear. In fact, the same mathematical description resurfaced within the new fundamental paradigm as ‘weak isospin’, which is a property of quarks that is conserved in weak interactions — a testament to how deeply embedded the language of spin seems to be in the workings of the world. Richard Webb, Senior Editor, Nature News & Views ORIGINAL RESEARCH PAPERS Heisenberg, W. Über den Bau der Atomkerne. Z. Phys. 77, 1–11 (1932) | Yukawa, H. On the interaction of elemen- tary particles. Proc. Phys. Math. Soc. Jap. 17, 48–57 (1935) | Wigner, E. On the consequences of the symmetry of the nuclear Hamiltonian on the spectroscopy of nuclei. Phys. Rev. 51, 106–119 (1937) | Yang, C. N. & Mills, R. L. Conservation of isotopic spin and isotopic gauge invariance. Phys. Rev. 96, 191–195 (1954) | Gell-Mann, M. Symmetries of baryons and mesons. Phys. Rev. 125, 1067–1084 (1962) fuRtHER REAdING Wigner, E. The unreason- able effectiveness of mathematics in the natural sciences. Comm. Pure Appl. Math. 13, 1–14 (1960) | Robson, D. Isospin in nuclei. Science 179, 133–139 (1973) | Warner, D. D., Bentley, M. A. & Van Isacker, P. The role of isospin symmetry in collective nuclear structure. Nature Phys. 2, 311–318 (2006) | Anderson, R. & Joshi, G. C. Interpreting mathematics in physics: charting the applications of SU(2) in 20th century physics, arXiv.org [online] <http://arxiv.org/PS_cache/ physics/pdf/0605/0605012v1.pdf> (2006) heisenberg proposed a model that counted up all the spins and included the exchange interaction between nearest neighbours only; for example, in a linear chain of spins, only two neighbouring spins would count, in a square lattice, four. When these were summed, heisenberg found a ground state (lowest-energy configuration) in which all the spins of the electronslined up in parallel — that is, a ferromagnetic state without the need for any external magnetic field. May Chiao, Senior Editor, Nature Physics ORIGINAL RESEARCH PAPERS Heisenberg, W. Zur Theorie des Ferromagnetismus. Z. Phys. 49, 619–636 (1928) | Dirac, P. A. M. Quantum mechanics in many-electron systems. Proc. R. Soc. Lond. A 123, 714–733 (1929) fuRtHER REAdING Mott, N. & Peierls, R. Werner Heisenberg. 5 December 1901–1 February 1976. Biogr. Mem. Fellows R. Soc. 23, 212–251 (1977) The Dirac equation is monumental in physics, encapsulating so beautifully, in relativistic terms, the behaviour of a spinning electron, or indeed of any particle that has half-integer spin (Milestone 4). Wolfgang Pauli — on whose ideas the concept of a spinning electron was based — was impressed by the mathematical ‘acrobatics’ of Paul Dirac in arriving at the succinct expression, published in 1928, but he was not, however, satisfied. Pauli questioned the reliance of Dirac’s theory on the exclusion principle and the emphasis on a half-unit of spin — why should nature permit only half units? With Victor Weisskopf, Pauli set about resurrecting the Klein–Gordon equation, which describes a particle that has zero spin, but which had been all but abandoned following the unsuccessful attempt by Erwin Schrödinger in 1926 to build it into a theory of quantum-wave mechanics. Weisskopf and Pauli, however, succeeded in quantizing the Klein–Gordon equation to obtain spin-0 particles of both negative and positive charge — just as Dirac had obtained spin-1/2 particles of negative and positive charge from his equation. These spin-0 particles, moreover, did not obey the exclusion principle. Dirac’s ‘positive electron’ — the positron — was discovered (although not immediately recognized as such) by Carl Anderson in 1932, the same year that James Chadwick discovered the neutron; in 1935, Hideki Yukawa postulated the existence of the meson, and the muon was discovered in 1936. There was suddenly a growing family of particles to describe, alongside the electron, proton and photon. It was thinking about how to reconcile the Klein–Gordon and Dirac equations, and the existence of all these particles (how many more might be discovered?) that led Pauli to one of the most subtle concepts of modern physics — the spin–statistics theorem. In his 1940 paper, Pauli identified a vital connection between spin and quantum statistics (in the 1920s, it had been realized that something more than the Maxwell–Boltzmann variety was needed at the quantum level). According to Pauli, particles of half-integer spin obey Fermi–Dirac statistics (and, hence, are now called ‘fermions’) and those of integer spin obey Bose–Einstein statistics (‘bosons’). Mathematically speaking, the quantization of fields with half-integer spin relies on ‘plus’ commutation relations, whereas that of fields with integer spin uses ‘minus’ commutation relations. Put another way, the wavefunction of a system of bosons is symmetric if any pair of bosons is interchanged, but is antisymmetric for interchanged particles in a system of fermions. Subtle indeed, but from Pauli’s spin–statistics connection arises the exclusion principle for fermions, with its implications for atomic structure, and a ‘non-exclusion’ principle for bosons — many bosons can adopt the same quantum state at once, as happens in a Bose–Einstein condensate. Further particle discoveries since 1940 and the subsequent building of the ‘standard model’ have also served to confirm that nature works with both integer and half-integer spins. Alison Wright, Chief Editor, Nature Physics ORIGINAL RESEARCH PAPERS Pauli, W. & Weisskopf, V. F. Über die Quantisierung der skalaren relativistischen Wellengleichung. Helv. Phys. Acta 7, 709–731 (1934) | Pauli, W. The connection between spin and statistics. Phys. Rev. 58, 716–722 (1940) fuRtHER REAdING Duck, I. & Sudarshan, E. C. G. Toward an understanding of the spin–statistics theorem. Am. J. Phys. 66, 284–303 (1998) | Tomonaga, S. The Story of Spin (Univ. Chicago Press, Chicago, 1997) m I L E S tO N E 7 Vital statistics Mi los luz | D rea ms tim e.c om According to Pauli, particles of half-integer spin obey Fermi–Dirac statistics and those of integer spin obey Bose–Einstein statistics. Milestones Nature MILeStONeS | Spin March 2008 | S9 © 2008 Nature Publishing Group If, during the 1920s and 1930s, the atomic nucleus had seemed of interest to few besides the (mostly) gentleman scientists studying it, by the end of the Second World War its wider importance was abundantly clear. The coming of the nuclear age was an appropriate cue for the two papers that cleared the way for arguably the most widespread practical application of nuclear spin today: nuclear m I L E S tO N E 8 New resonance magnetic resonance (NMR) spectroscopy. The 1946 work of Edward Mills Purcell at the Massachusetts Institute of Technology and Felix Bloch at Stanford University gave new relevance to one object of intense gentlemanly interest before the war: the Zeeman splitting of nuclear spin states in a magnetic field (Milestone 1). The degree of splitting at a particular magnetic field strength depends on the gyromagnetic ratio of the nucleus. In NMR, a second, transverse field at the characteristic (typically radio) spin-transition frequency produces an absorption resonance — a powerful way to identify the nuclei present in a sample. Purcell et al. brought protons (1H) in solid paraffin to resonance; Bloch et al. did the same in liquid water. The coincident timing was no accident: the development of radar technologies during the war, for which several of the researchers involved had won their spurs, had made sources of radiofrequency radiation freely available for the first time. The effect itself was not entirely new. In 1938, Isidor Rabi had used it to measure magnetic moments of both atomic species in a lithium chloride molecular beam, receiving the 1944 Nobel Prize in Physics for that advance. Even earlier, the Dutch physicist Cornelis J. Gorter had looked for the resonance of 7Li in lithium fluoride and 1H in alum, using a calorimetric method. Hampered by experimental vagaries and limited resources, he published a negative result. (In later years, on receiving a prize for his contributions to low-temperature physics, Gorter would muse on his strange ability to miss out on groundbreaking discoveries in this and other instances.) The innovations offered by Bloch and Purcell’s approaches were the transition to real liquid and solid systems, and, in Bloch’s case, the use of an induction coil to pick up and sharpen the resonance signal. These opened the way for the use of NMR in all manner of contexts, including in living tissue — where it became the lynchpin of magnetic resonance imaging (Milestone 15). In 1944, although shielded in the relative obscurity of Kazan in the steppes of Tatarstan, the Soviet physicist Yevgeny Zavoisky published the first measurements of an analogous effect involving electron spins. Electron paramagnetic resonance depends on an atom possessing an unpaired electron, m I L E S tO N E 9 From the compass to Apollo Long before the concept of spin had been realized, the phenomenon of magnetism was a source of fascina- tion and curiosity. the first scientific record of magnetism was made by the Greek philosopher thales of Miletos, who, in the sixth century bc, studied the attraction of materials such as iron to loadstone (magnetite). the first magnetic device was, of course, the compass — probably invented by several cultures inde- pendently and first documented in chinese literature in the eleventh century ad. Nearly a millennium later, and particularly since the 1950s, devices based on magnetism are once more proving significant in shaping our way of life. the magnetic tape, whichwas invented in 1878 by Oberlin Smith, was commercialized in the 1930s by aeG and BaSF. In later decades, it was developed into, for example, videotape in 1951 and the magnetic stripes on credit cards in the 1960s. Following the invention of mod- ern computers, technology similar to magnetic tape was the logical choice for long-term data storage. the first hard drive with a moveable head was built into the IBM 305 computer, which shipped in 1956. Its large hard disks — 24 inches in diameter — had a storage density of 2 kilobits per square inch. IBM was also a pioneer in the development of the removable floppy disk. the first floppy disk, which had a diameter of 8 inches and a storage capacity of about 80 kilobytes, dates from 1969. the cumbersome 8-inch format was soon brought down in size: the last popular format was the Sony 3.5-inch floppy. Magnetism has also been the key to several other, historical, storage techniques. the earliest was the ‘drum memory’ in the 1950s, which consisted of rotating circular metallic plates coated with a magnetic mate- rial. Drum memory was superseded in the 1960s by the ‘core memory’ — a hand-woven grid of wires with small ferrite rings (the cores) at the intersections. complex current pulses First NMR signals from water. Image reprinted with permission from Bloch, F., Hansen, W. W. and Packard, M. Phys. Rev. 70, 474–485 (1946). Courtesy of the American Physical Society. The coming of the nuclear age was an appropriate cue… for arguably the most widespread practical application of nuclear spin today. Magnetic core random access memory. Image courtesy of H. J. Sommer III, Professor of Mechanical Engineering, Penn State University. Milestones S10 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group http://en.wikipedia.org/wiki/Magnetic_core_memory thereby limiting the range of its application, but making it useful for the detection and identification of free radicals. Zavoisky might also have been the first to see an NMR signal, but he did not follow it up, at least not with publications. Had the vicissitudes of the age been less, and the dissemination of scientific information easier, his claim might have been better heard in the West. As it was, the 1952 Nobel Prize in Physics went to Bloch and Purcell. Richard Webb, Senior Editor, Nature News & Views ORIGINAL RESEARCH PAPERS Gorter, C. J. Negative results of an attempt to detect nuclear magnetic spins. Physica 9, 995–998 (1936) | Rabi, I. I., Zacharias, J. R., Millman, S. & Kusch, P. A new method of measuring nuclear magnetic moment. Phys. Rev. 53, 318 (1938) | Zavoisky, E. Relaxation of liquid solutions for perpendicular fields. J. Phys. USSR 9, 211–216 (1945) | Purcell, E. M., Torrey, H. C. & Pound, R. V. Resonance absorption by nuclear magnetic moments in a solid. Phys. Rev. 69, 37–38 (1946) | Bloch, F., Hansen, W. W. & Packard, M. Nuclear induction. Phys. Rev. 69, 127 (1946) | Zavoisky, E. Spin magnetic resonance in the decimetre-wave region. J. Phys. USSR 10, 197–198 (1946) fuRtHER REAdING Gorter, C. J. Bad luck in attempts to make scientific discoveries. Phys. Today 20 (1), 76–81 (1967) | Kochelaev, B. I. & Yablokov, Y. V. The Beginning of Paramagnetic Resonance (World Scientific, Singapore, 1995) Nuclear magnetic resonance (NMR) spectroscopy (Milestone 8) is one of the most powerful analytical techniques in modern chemistry — a window into the world of molecules that can provide information about their structures, dynamic behaviour and how they interact with one another. Prior to the 1950s, the study of NMR was rooted firmly in the physics community. It was assumed that the frequency at which a given nucleus resonated depended only on the strength of the magnetic field in which it was placed. Physicists therefore anticipated that they could use the technique to measure — with unprecedented precision — the magnetic moments of different nuclei. When, in 1950, Warren Proctor and Fu Chun Yu set out to do this for 14N, something unexpected happened. For their experiments, they chose the compound ammonium nitrate (NH4NO3), which is highly soluble in water and contains two nitrogen nuclei per molecule — factors that were expected to improve the NMR signal. In what they described as a “surprising observation”, however, not one but two resonance frequencies were detected — one for the nitrogen nuclei in the ammonium (NH4+ ) ions and the other for those in the nitrate (NO3– ) ions. This was the first reported observation of the phenomenon that soon became known as ‘chemical shift’, in which the local chemical environment surrounding a nucleus influences the frequency at which it resonates. The implications of NMR for the structural analysis of organic compounds became apparent soon afterwards, when, in 1951, a group of researchers from Stanford University showed that different 1H nuclei in the same molecule resonate at different frequencies. James Arnold, Srinivas Dharmatti and Martin Packard demonstrated the huge potential of NMR spectroscopy by applying the technique to ethanol (CH3CH2OH), a compound in which each molecule comprises three sets of non-equivalent 1H nuclei. Using tiny sample volumes and placing them in the most uniform region within a magnetic field, they obtained a spectrum displaying three separate lines, corresponding to the resonant frequencies of the 1H nuclei in the CH3, CH2 and OH groups, respectively. Moreover, the relative intensities of the three signals corresponded with the number of protons in each different chemical environment. So it was possible not only to identify different molecular fragments but also to glean quantitative information about the number of equivalent nuclei in each. Later in 1951, Herbert Gutowsky and David McCall showed that different spin-active nuclei in the same molecule interact with one another, giving rise to fine structure in the NMR signals that encodes a wealth of information regarding molecular connectivity and structure. It did not take the chemistry community long to embrace the technique for the spectroscopic analysis of compounds. Techniques using radio- frequency pulses — rather than a continuous source — broadened the scope of NMR spectroscopy, and Fourier-transform methods of data processing notably improved the sensitivity of the method. The combination of these advances allowed the development of sophisticated multi- dimensional NMR experiments that revolutionized the field (Milestone 16). Stuart Cantrill, Chief Editor, Nature Chemistry ORIGINAL RESEARCH PAPERS Proctor, W. G. & Yu, F. C. The dependence of a nuclear magnetic resonance frequency upon chemical compound. Phys. Rev. 77, 717 (1950) | Hahn, E. L. Spin echoes. Phys. Rev. 80, 580–594 (1950) | Arnold, J. T., Dharmatti, S. S. & Packard, M. E. Chemical effects on nuclear induction signals from organic compounds. J. Chem. Phys. 19, 507 (1951) | Gutowsky, H. S. & McCall, D. W. Nuclear magnetic resonance fine structure in liquids. Phys. Rev. 82, 748–749 (1951) | Carr, H. Y. & Purcell, E. M. Effects of diffusion on free precession in nuclear magnetic resonance experi- ments. Phys. Rev. 94, 630–638 (1954) | Ernst, R. R. & Anderson, W. A. Application of Fourier transform spectroscopy to magnetic reso- nance. Rev. Sci. Instrum. 37, 93–102 (1966) | Aue, W. P., Bartholdi, E. & Ernst, R. R. Two dimensional spectroscopy. Application to nuclear magnetic resonance. J. Chem. Phys. 64, 2229–2246 (1976) fuRtHER REAdING Becker, E. D. Magnetic resonance: an account of some key discoveries and their consequences. Appl. Spectrosc. 50, 16A–28A (1996) m I L E S tO N E 1 0 A shift in expectations through the wires were able to read, as well as set, the magnetization of the cores. Despite being an intricate device, a core memory of two cubic feet, with a capacity of 4,096 words, wasused in the apollo guidance com- puter, onboard the NaSa missions to the Moon. computer memory was miniaturized further in the late 1970s, for example using ‘bubble memory’ in which data storage is based on small magnetic domains on a thin film. Soon afterwards, hard drives became the dominant data-storage system for computers. the history of magnetic devices illustrates well how, with a little inventiveness, the macroscopic manifestations of magnetism can be harvested to achieve amazing techno- logical advances. however, it would take a more fundamental under- standing of spin physics to achieve the next technological revolution in computing and information storage (Milestone 18). Joerg Heber, Senior Editor, Nature Materials Paolotoscani | Dreamstime.com Milestones Nature MILeStONeS | Spin March 2008 | S11 © 2008 Nature Publishing Group In 1935, albert einstein, Boris Podolsky and Nathan rosen ques- tioned whether quantum mechanics fully describes ‘physical reality’. their paper, which was intended to illustrate that quantum mechanics is incomplete, sparked discussions that go deep into the philosophical aspects of ‘reality’ and how phys- ics can describe it. Later that year, einstein confessed in a letter to erwin Schrödinger that he felt that “the main point was, so to speak, buried by erudition”, and began publishing his own versions of the ‘incompleteness argument’. all of these accounts, and the original einstein–Podolsky–rosen paper, made their point using continuous variables — that is, position and momentum. however, the version that is most widely discussed in the modern literature, and also forms m I L E S tO N E 1 1 Mind-boggling reality Impurities are not always unwanted. With the right type and dose of impurity atoms, the bulk properties of a material can be tuned in a beneficial way, which is a technique made heavy use of, for example, in standard silicon technology. At the microscopic level, interesting questions arise about how an impurity atom interacts with its host. In 1964, Jun Kondo resolved a long-standing question regarding the electrical resistance of magnetic impurity-doped metals. The mystery was this: the resistance of a metal should decrease with decreasing temperature, as atomic vibrations freeze out, so that conduction electrons can move more easily through the material; however, for magnetically doped metals, the resistance was found to increase again below a certain temperature. Kondo discovered that it is the intrinsic spin of magnetic impurity atoms that leads to this anomalous resistance. The amount of scattering that electrons experience at the impurities does not decrease but increases when the temperature goes down, and this leads to the observed minimum in total resistance. Not only did this finding explain a nagging problem but it also triggered a vast amount of theoretical follow-up work. The initial issue to tackle was that the effect seemed to yield infinite resistance as zero temperature is approached — clearly an unphysical result. It was soon found that this divergence of resistance is suppressed, below a certain temperature (the Kondo temperature), by the formation of a bound state between impurity and conduction electrons, in which electron spins line up to screen the spin of the impurity atom. A later development was m I L E S tO N E 1 2 Odd one out the extension of the theory to ‘Kondo lattices’ in which electrons interact not only with the odd magnetic impurity but rather with an array of localized spins, and are significantly slowed down by the strong interactions. This model can explain some of the unusual properties, such as anomalous superconductivity, displayed by so-called heavy-fermion compounds. Another line of research is the Kondo effect in nanometre-sized structures, such as quantum dots, in which the interactions between a single magnetic impurity and its environment can be controlled. A quantum dot can be tuned to contain an odd number of electrons — that is, an unpaired spin. Below the Kondo temperature, this localized spin can form a bound state with the free electrons in the electrodes on either side of the quantum dot, similar to the classical Kondo effect. However, this ‘Kondo resonance’ opens an additional pathway for electrons to flow through the quantum dot and, as a result, the resistance decreases, in contrast to the original effect. Jun Kondo. Image courtesy of AIST, Tokyo. the basis of many experimental investigations, presents the argu- ment in a simpler and clearer form, in terms of discrete spin variables. It was penned by David Bohm and appeared originally in his 1951 book Quantum Theory; he developed the argument further, in the context of experimental proofs, with Yakir aharonov in 1957. Bohm and aharonov considered a molecule made of two atoms — each having one half-unit of spin — combined such that the total spin of the molecule is zero. When the two atoms are separated, and, for one of the spins, the spin component is measured along a given direction, the same component is immediately known for the other spin — it is exactly the opposite, as the total spin still has to be zero. at first sight, it might not seem surprising that infor- mation about the properties of the second particle of a composite system can be deduced without performing any measurement on it, and without any interaction between the two par- ticles, if the initial condition restricts how the two particles behave with respect to each other. For a quantum spin, however, the situation is more subtle. Quantum mechanics allows only one compo- nent of the spin to have a definite value. If, for instance, the x component of the spin is known, then the components along the y and z axes must be indeterminate; the component that is definite is determined by its measurement. Yet, in this case of two separated spin-1/2 particles, an experimenter can decide at the last minute — long after the two constituents have been separated — along which direction the first spin is measured. and this choice has immediate consequences on which component of the second, unobserved, spin is definite. how can the second spin know what has been done to the first? Is there some kind of hidden interac- tion that quantum theory does not account for? Does quantum mechan- ics allow what einstein famously called “spooky action at a distance” (an idea he did not like)? einstein argued that if no action at a distance can instantaneously influence the second spin, then it must have had all its components well defined from the David Bohm. Image from Library of Congress, New York — Telegram and Sun Collection, courtesy of AIP Emilio Segrè Visual Archives. S12 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group The way that spin is woven into the very fabric of the Universe is writ large in the standard model of particle physics. In this model, which took shape in the 1970s and can explain the results of all particle-physics experiments to date, matter (and antimatter) is made of three families of quarks and leptons, which are all fermions, whereas the electromagnetic, strong and weak forces that act on these particles are carried by other particles, such as photons and gluons, which are all bosons. Despite its success, the standard model is unsatisfactory for a number of reasons. First, although the electromagnetic and weak forces have been unified into a single force, a ‘grand unified theory’ that brings the strong interaction into the fold remains elusive. Second, the origins of mass are not fully understood. Third, gravity is not included. Moreover, there are other, less obvious problems with the standard model. The two natural mass scales in nature are zero and the Planck mass, ~ 1019 GeV c−2. Neither photons nor gluons(which carry the electromagnetic and strong forces, respectively) have mass, but the W and Z bosons that are responsible for the weak force have masses of about 90 GeV c−2. Where does this mass scale come from? This ‘hierarchy problem’ can be solved by fine- tuning the model so that various quantum fluctuations cancel out, although many physicists are uncomfortable with this solution because some parameters must be fine-tuned to better than 1 part in 1015. However, a form of symmetry between fermions and bosons called supersymmetry offers a much more elegant solution because the quantum fluctuations caused by bosons are naturally cancelled out by those caused by fermions and vice versa. Symmetry plays a central role in physics. The fact that the laws of physics are, for instance, symmetric in time (that is, they do not change with time) leads to the conservation of energy. These laws are also symmetric with respect to space, rotation and relative motion. Initially explored in the early 1970s, supersymmetry is a less obvious kind of symmetry, which, if it exists in nature, would mean that the laws of physics do not change when bosons are replaced by fermions, and fermions are replaced by bosons. Although it is difficult to explain supersymmetry through analogies to classical physics, its consequences are dramatic — it predicts that every fundamental particle has a superpartner with half a unit of spin less. The electron, for instance, has a spin of a half, so its superpartner (which is known as a selectron) has zero spin. This means that the superpartner of a boson is always a fermion and vice versa. Supersymmetry also plays a central role in theories that attempt to unify the forces in the standard model with gravity by treating fundamental particles as vibrating strings or membranes in 10-dimensional or 11-dimensional spacetimes. In these theories the gravitational force is carried by a spin-two boson called the graviton. Searching for supersymmetric particles will be a priority when the Large Hadron Collider comes into operation at CERN, the European particle-physics laboratory near Geneva, in 2008. Peter Rodgers, Chief Editor, Nature Nanotechnology ORIGINAL RESEARCH PAPERS Golfand, Y. A. & Likhtman, E. P. Extension of the algebra of Poincaré group generators and viola- tion of P invariance. JETP Lett. 13, 323–326 (1971) | Neveu, A. & Schwarz, J. H. Factorizable dual model of pions. Nucl. Phys. B 31, 86–112 (1971) | Ramond, P. Dual theory for free fermions. Phys. Rev. D 3, 2415–2418 (1971) | Wess, J. & Zumino, B. Supergauge transformations in four dimensions. Nucl. Phys. B 70, 39–50 (1974) | Wess, J. & Zumino, B. A Lagrangian model invariant under super- gauge transformations. Phys. Lett. B 49, 52–54 (1974) fuRtHER REAdING Dimopoulos, S., Raby, S. & Wilczek, F. Supersymmetry and the scale of unification. Phys. Rev. D 24, 1681–1683 (1981) | Almadi, U., de Boar, W. & Furstenau, H. Comparison of grand unified theories with electroweak and strong coupling constants measured at LEP. Phys. Lett. B 260, 447–455 (1991) | Greene, B. The Elegant Universe (Vintage, London, 2000) | Kane, G. & Shifman, M. (eds) The Supersymmetric World: The Beginnings of the Theory (World Scientific, Singapore, 2000) m I L E S tO N E 1 3 Super symmetry The ATLAS experiment under construction at the Large Hadron Collider. Image courtesy of CERN. The ideas and methods developed by Kondo and his fellow theorists turned out to be relevant to a wide range of problems that involve strong interactions between particles. As a result, the ‘Kondo effect’ — which, in truth, comprises a range of phenomena to do with collective behaviour arising from localized magnetic impurities — is an active research topic today and one that still throws up surprises. Liesbeth Venema, Senior Editor, Nature ORIGINAL RESEARCH PAPERS Kondo, J. Resistance minimum in dilute magnetic alloys. Prog. Theor. Phys. 32, 37–49 (1964) | Anderson, P. W. A poor man’s derivation of scaling laws for the Kondo problem. J. Phys. C 3, 2346–2441 (1970) | Goldhaber-Gordon, D. et al. Kondo effect in a single-electron transistor. Nature 391, 156–159 (1998) fuRtHER REAdING Wilson, K. G. The renormalization group: critical phenomena and the Kondo problem. Rev. Mod. Phys. 47, 773–840 (1975) | Tsvelik, A. M. & Wiegmann, P. B. Exact results in the theory of magnetic alloys. Adv. Phys. 32, 453–713 (1983) | Kouwenhoven, L. & Glazman, L. Revival of the Kondo effect. Phys. World 14(1), 33–38 (2001) outset — hence, quantum mechanics must be incomplete. a decisive step came in 1964 when John Bell, building on the Bohm–aharonov formulation in spin variables, showed that quantum mechanics makes predictions that contradict the local-realistic world view of einstein and do require action at a distance of some sort. Bell’s theorem has been put to the test many times since, and although there is, as yet, no single experiment that closes all possible loopholes, the weight of evidence does still favour quantum mechanics. Andreas Trabesinger, Senior Editor, Nature Physics ORIGINAL RESEARCH PAPERS Einstein, A., Podolsky, B. & Rosen, N. Can quantum- mechanical description of physical reality be considered complete? Phys. Rev. 47, 777–780 (1935) | Bohm, D. Quantum Theory Ch. XXII (Prentice-Hall, Englewood Cliffs, New Jersey, 1951) | Bohm, D. & Aharonov, Y. Discussion of experimental proof for the paradox of Einstein, Rosen, and Podolsky. Phys. Rev. 108, 1070–1076 (1957) | Bell, J. S. On the Einstein Podolsky Rosen paradox. Physics 1, 195–200 (1964) fuRtHER REAdING Bell, J. S. Bertlmann’s socks and the nature of reality. J. Phys. 42, 41–62 (1981) | Sauer, T. An Einstein manuscript on the EPR paradox for spin observables. Stud. Hist. Philos. Mod. Phys. 38, 879–887 (2007) Nature MILeStONeS | Spin March 2008 | S13 © 2008 Nature Publishing Group the fact that a dirty metal can support an electric current flowing without resistance might sound exotic to some, but it is a textbook property of ‘conventional’ superconductors. When spins are involved, however, the super- conductors do become ‘exotic’. the conventional mechanism of superconductivity was explained by John Bardeen, Leon cooper and robert Schrieffer (in what is known as the BcS theory) back in 1957. For decades, it was a mystery how electrons, which are classified as ‘fermions’, could be forced into a single ground state that was more typical for ‘bosons’ (as when they undergo Bose–einstein condensation). Fermions cannot all pile into the same ground state because only two — one with its spin pointing upwards and the other pointing downwards — can occupy each quantum state; bosons do not heed such conventions. as it turns m I L E S tO N E 1 4 Sticking together The scientific principles of magnetic resonance imaging (MRI) stem from those of nuclear magnetic resonance (NMR; Milestone 8); however, now, especially in the mind of the public, the latter lies very much in the shadow of the former. The technological jump from NMR spectrum to MR image began in the early 1970s, and subsequent developments have established MRI as a priceless technique in medical research and diagnostics. MRI uses magnetic fields and radiowaves to produce, in a non-invasive manner, ‘tomographic’ images of a three-dimensional object. Paul Lauterbur introduced the scientific basis behind this mode of visualization as “image formation by induced local interactions”. His idea was to combine two magnetic fields, so that one induces an interaction whereas the other restricts this interaction to a localized region in space. He proposed the term ‘zeugmatography’ to describe the technique, from a Greek word meaning ‘that which is used for joining’; however, the name never became widely accepted. Lauterbur’s pioneering experiment involved the imaging of a cross-section throughtwo glass tubes of ordinary water (H2O) attached to the inside wall of a larger tube of deuterated water (D2O). A two-dimensional image m I L E S tO N E 1 5 From spectrum to snapshot showing the location of the tubes of H2O was generated by combining four projections taken from different angles around the set-up. Some scepticism surrounded this initial observation. It seemed counterintuitive that radiowaves could be used to image objects that were much smaller than their wavelength. Yet it was because the interactions were restricted to certain regions that, in fact, the technique became independent of wavelength. Lauterbur recognized the potential of the concept at the time of the first simple experiment. He believed it could be used to investigate complex systems and noted the possibility of visualizing biological tissues — in particular, distinguishing between malignant tumours and healthy tissue. Many of the early practical developments in MRI were made by Peter Mansfield, who discovered how to acquire images rapidly. In recognition of their contributions, Lauterbur and Mansfield shared the 2003 Nobel Prize in Medicine. The invention of MRI has not been without controversy. Others have claimed to have produced the first out, the only way for fermions to form a condensate is for them to pair up, with the help of the crystalline lattice: when one electron passes through the lattice, the positive ions are slightly attracted to the passing negative elec- tron; if a second electron comes along, it will sense the deformed lattice and be attracted to the net positive charge, and hence to the original electron. this kind of lattice-assisted coupling is weak, but it is strong enough for the paired electrons to drop down to a collective ground state. Naturally, people considered whether such pairing could glue other fermions together, in particular 3he. as 4he exhibits superfluidity — that is, the liquid can flow without viscosity below a certain temperature — it was believed (hoped) that 3he would do likewise. Yet, given that 4he is a boson and 3he is a fermion, it was not clear how 3he could condense until the BcS theory came along. however, the magnetic interactions between the 3he particles are strong, and so they cannot pair up as electrons do. Instead, the pairing glue must come from another source. the first authors to propose ferromagnetic fluctuations of the spins as such a glue were a. Layzer and D. Fay. When one particle whizzes through the liquid, its spin (pointing upwards, for instance) attracts other spin-up particles and repels spin-down particles. the effec- tive spin-up polarization can then attract another spin-up particle, lead- ing to a spin-up–spin-up pair. When coupled in this way, the 3he atoms are able to form a superfluid. amazingly, all the theoretical groundwork, including that by Philip anderson and Pierre Morel, and by roger Balian and richard Werthamer, was laid down before the experimental confirma- tion of a superfluid state in 3he — that came in 1972 and earned its authors, Douglas Osheroff, robert richardson and David Lee, the Nobel prize in Physics in 1996. although superfluidity was antici- pated, measurements revealed several unique superfluid phases in 3he. Moreover, because of the non-zero spin of the pairs (in conventional superconductors the net spin is zero), Milestones S14 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group In the mid-1970s, major advances in solution nuclear magnetic resonance (NMR) spectroscopy set the stage for a revolutionary new application: solving the three-dimensional (3D) structures of proteins in the solution state. At the time, X-ray crystallography was already a well-established tool for the determination of protein crystal structures. Unlike crystallography, NMR does not require proteins to form diffracting crystals and this broadens the range of proteins that can be investigated. Furthermore, most proteins exist naturally in a solution state, or in contact with fluids, so knowledge of their properties in their native environment has physiological relevance. A unique strength of NMR is its ability to supplement molecular structures with information on dynamic processes, which may be influenced, for example, by ligand binding in solution: even before structure determination by NMR became feasible, the technique was used to obtain information about protein dynamics. In 1971, Adam Allerhand and colleagues demonstrated the existence of sub-nanosecond segmental motions in proteins, and by the middle of the decade, the groups of Brian Sykes, Robert J. P. Williams and Kurt Wüthrich presented evidence for lower-frequency motions in globular proteins. Two fundamental advances in the late 1970s set the scene for the development of NMR into a method for determining previously unknown protein structures (rather than refining incomplete structures). First, Richard Ernst, building on a breakthrough idea by Jean Jeener, demonstrated the principle of two-dimensional (2D) NMR spectroscopy. This technique, which also applies to other spectroscopies, allowed researchers to record not only chemical shifts (Milestone 10) but also the interactions between pairs of nuclear spins — it later won Ernst the 1991 Nobel Prize in Chemistry. Second, Wüthrich discovered that the nuclear Overhauser effect could be exploited in NMR experiments with proteins, allowing the mapping of networks of near-by atom pairs that are not connected through covalent bonds. Beginning in 1976, Wüthrich and Ernst joined forces, and with Kuniaki Nagayama and Anil Kumar they developed a number of 2D NMR experiments, which became the basis for solving protein structures. In 1982, Gerhard Wagner and Wüthrich published the sequence-specific assignments for a small protein, basic pancreatic trypsin inhibitor. Meanwhile, Werner Braun and Timothy Havel in the Wüthrich group were developing algorithms and software capable of calculating protein structures from NMR data. In 1985, Michael Williamson, Havel and Wüthrich reported the first solution-state protein structure — that of proteinase inhibitor IIA from bull seminal plasma. The results were met with disbelief. It was not until several structures solved initially using NMR were solved again using crystallography that the NMR technique was accepted. In 2002, Wüthrich was rewarded with the Nobel Prize in Chemistry. NMR has become a powerful technique for protein structure determination. Numerous advances made during the past two decades — including the development of three- and four- dimensional spectroscopy, isotope labelling methods, and increases in magnetic field strength — have raised the limit on the size of proteins that can be investigated. Currently, about 10% of structures being deposited in the Protein Data Bank are solved using NMR. Perhaps the most exciting frontier is the application of NMR to investigate protein dynamics, especially for large molecular machines, which will undoubtedly lead to new insights in biology. Allison Doerr, Associate Editor, Nature Methods ORIGINAL RESEARCH PAPERS Allerhand, A. et al. Conformation and segmental motion of native and denatured ribonuclease A in solution. Application of natural-abundance carbon-13 partially relaxed Fourier transform nuclear magnetic resonance. J. Am. Chem. Soc. 93, 544–546 (1971) | Wüthrich, K. & Wagner, G. NMR investigations of the dynamics of the aromatic amino acid residues in the basic pancreatic trypsin inhibitor. FEBS Lett. 50, 265–268 (1975) | Dobson, C. M., Moore, G. R. & Williams, R. J. P. Assignment of aromatic amino acid PMR resonances of horse ferricytochrome c. FEBS Lett. 51, 60–65 (1975) | Snyder, G. H., Rowan, R. & Sykes, B. D. Complete tyrosine assignments in the high-field proton nuclear magnetic resonance spectrum of bovine pancreatictrypsin inhibitor selectively reduced and carboxamidomethylated at cystine 14-38. Biochemistry 15, 2275–2283 (1976) | Aue, W. P., Bartholdi, E. & Ernst, R. R. Two-dimensional spectroscopy. Application to nuclear magnetic resonance. J. Chem. Phys. 64, 2229–2246 (1976) | Nagayama, K., Wüthrich, K., Bachmann, P. & Ernst, R.R. Two-dimensional J-resolved 1H NMR spectroscopy for studies of biological macromolecules. Biochem. Biophys. Res. Commun. 78, 99–105 (1977) | Kumar, A., Ernst, R. R. & Wüthrich, K. A two-dimensional nuclear Overhauser enhancement (2D NOE) experiment for the elucidation of complete proton–proton cross-relaxation networks in biological macromolecules. Biochem. Biophys. Res. Commun. 95, 1–6 (1980) | Wagner, G. & Wüthrich, K. Sequential resonance assignments in protein 1H nuclear magnetic resonance spectra: basic pancreatic trypsin inhibitor. J. Mol. Biol. 155, 347–366 (1982) | Williamson, M. P., Havel, T. F. & Wüthrich, K. Solution conformation of proteinase inhibitor IIA from bull seminal plasma by 1H nuclear magnetic resonance and distance geometry. J. Mol. Biol. 182, 295–315 (1985) m I L E S tO N E 1 6 Solution for solution structures ‘NMR image’, most notably Raymond Damadian, who had reported in 1971 the ability to distinguish between normal tissue and tumours using magnetic resonance. On the announcement of the prize, he fervently disputed the decision of the Nobel committee. The unquestionable fact remains that, although the invention of MRI — with its marriage of magnetic fields — took scientists by surprise at its conception, in its more recent lifetime it has proved to be an invaluable tool for the medical world. Alison Stoddart, Associate Editor, Nature Materials ORIGINAL RESEARCH PAPERS Damadian, R. Tumor detection by nuclear magnetic resonance. Science 171, 1151–1153 (1971) | Lauterbur, P. C. Image formation by induced local interactions: examples employing nuclear magnetic resonance. Nature 242, 190–191 (1973) | Mansfield, P. & Grannell, P. K. NMR ‘diffraction’ in solids? J. Phys. C 6, L422–L426 (1973) | Mansfield, P., Garroway, A. N. & Grannell, P. K. Image formation in NMR by a selective irradiative process. J. Phys. C 7, L457–L462 (1974) | Mansfield, P. Multi-planar imaging formation using NMR spin echoes. J. Phys. C 10, L55–L58 (1977) 3he also yielded some unexpected properties. In 1987, a team working in Moscow discovered a pure spin supercurrent. unlike the supercur- rent in a conventional superconduc- tor that carries charge and mass, the spin supercurrent carries only spin and there is no mass flow. 3he is truly exotic, because of its spin. May Chiao, Senior Editor, Nature Physics ORIGINAL RESEARCH PAPERS Bardeen, J., Cooper, L. N. & Schrieffer, J. R. Microscopic theory of superconductivity. Phys. Rev. 106, 162–164 (1957) | Anderson, P. W. & Morel, P. Generalized Bardeen–Cooper–Schrieffer states and the proposed low-temperature phase of liquid He3. Phys. Rev. 123, 1911–1934 (1961) | Balian, R. & Werthamer, N. R. Superconductivity with pairs in a relative p wave. Phys. Rev. 131, 1553–1564 (1963) | Layzer, A. & Fay, D. Superconducting pairing tendency in nearly ferromagnetic systems. Int. J. Magn. 1, 135–141 (1971) | Osheroff, D. D., Richardson, R. C. & Lee, D. M. Evidence for a new phase of solid He3. Phys. Rev. Lett. 28, 885–888 (1972) | Osheroff, D. D., Gully, W. J., Richardson, R. C. & Lee, D. M. New magnetic phenomena in liquid He3 below 3 mK. Phys. Rev. Lett. 29, 920–923 (1972) | Borovik–Romanov, A. S., Bun’kov, Yu. M., Dmitriev, V. V. & Mukharskii, Yu. M. Observation of phase slippage during the flow of a superfluid spin current in 3He-B. JETP Lett. 45, 124–128 (1987) fuRtHER REAdING Leggett, A. J. A theoretical description of the new phases of liquid 3He Rev. Mod. Phys. 47, 331–414 (1975) Milestones Nature MILeStONeS | Spin March 2008 | S15 NMR has become a powerful technique for protein structure determination. © 2008 Nature Publishing Group m I L E S tO N E 1 8 A giant leap for electronics Towards the end of the 1960s, scientists had begun exploring the technological potential of magnetism combined with semiconductor physics. Having succeeded in introducing small amounts of magnetic impurities into otherwise non-magnetic semiconductors, Robert Gałazka and colleagues presented, in 1978, remarkable data on II–VI compounds doped with manganese. In these ‘diluted magnetic semiconductors’ (DMSs), the low- concentration defects (the manganese ions) did not compromise the quality of the material, meaning that its magneto- optical and magneto-transport properties could be probed. At the same time, pronounced magnetic properties could be observed — such as the spin splitting of electronic or impurity bands. A further breakthrough came in the early 1990s, with the advent of low- temperature molecular-beam epitaxy. By growing semiconductor films under conditions that were far from thermal equilibrium, it became possible to introduce manganese impurities into III–V materials (which is more difficult under equilibrium conditions owing to the low solubility of manganese). Hideo Ohno and colleagues then demonstrated, in 1992, ferromagnetic order in the DMS (In,Mn)As — indium arsenide containing only 1.3% manganese — by measuring magneto-transport and, in particular, an anomalous Hall effect in the material. The work was followed up, in 1996, with proof of ferromagnetism in doped gallium arsenide — (Ga,Mn)As — at temperatures up to 110 K. As GaAs can be used in electronic devices that operate at room temperature, these studies established the basis for research into ‘technologically relevant’ DMSs. The 1990s also brought theoretical work by Tomasz Dietl, in collaboration with Ohno’s group, which explained the origin of ferromagnetism in (Ga,Mn)As using a model developed, by Clarence m I L E S tO N E 1 7 Dilute for impact In retrospect, it seems surprising that, although spin and charge are two of the most fundamental properties of electrons, the advantage that could be gained from combining them in a consumer device was only realized in the 1990s, when IBM introduced a new type of hard-disk drive that would revolutionize data storage. Crucial to this technological revolution was an earlier discovery made by the groups of Albert Fert and Peter Grünberg — for which the two won the 2007 Nobel Prize in Physics. In 1988, they had observed a large change in the electrical resistance of thin metal layers as a function of an external magnetic field. Although bulk magnetoresistive effects had been known for more than a century (discovered by William Thomson, later to become Lord Kelvin), they were usually only moderate. However, in the studies led by Fert and Grünberg, the effect was much more pronounced. From the outset, these thin magnetic multilayer structures Zener in 1950, for ferromagnetism in transition metals. According to this model, the magnetic order originates from the delocalized holes that mediate the interaction between localized magnetic moments. The importance of the work was twofold. First, the carrier-mediated magnetic order suggested the possibility of controlling the ferromagnetism using electric fields — which was soon demonstrated — and, beyond that, the development of efficient spintronics devices. Second, the Dietl model provided an effective recipe for calculating the Curie temperature of other zinc-blende and wurzite semiconductors, to advance the search for a room-temperature DMS. In particular, Dietl showed that DMSs based on zinc oxide (ZnO) or gallium nitride (GaN) could have Curie temperatures as high as 300 K. Investigations since then have indeed revealed room-temperature ferromagnetism in oxides and semiconductors that include ZnO or GaN. However, it is yet to be proved that the carrier-mediated mechanism proposed by Dietlis really at work showed magnetoresistance of up to 50%; the phenomenon was dubbed ‘giant’ magnetoresistance (GMR). GMR is based on the spin-dependent scattering of electrons travelling across metallic thin films. In its most basic realization, a GMR device consists of two thin magnetic metal films, separated by a non-magnetic metal. If the magnetic layers have a different magnetic orientation with respect to each other, the electrons scatter strongly in the trilayer structure and the electrical resistance is high. However, once the magnetic orientation of the magnetic layers is aligned using an external magnetic field, electrons with spins antiparallel to that direction scatter much less, and move more easily between the magnetic and non-magnetic layers — hence, the electrical resistance is low. This groundbreaking discovery quickly led to the use of GMR to miniaturize the recording heads of hard-disk drives. IBM had already, in 1991, developed a hard drive based on the smaller bulk magnetoresistance effect; in 1997, thanks largely to the efforts of Stuart Parkin and colleagues in the IBM laboratories, the first hard drives based on GMR were commercialized. More recently, a new magnetoresistive Image courtesy of P. M. Koenraad, Eindhoven University of Technology. device has been incorporated into hard-disk drives — the magnetic tunnel junction. Magnetic tunnel junctions (introduced in 1975 by Michel Jullière) are similar in structure to the GMR trilayers, except that the metallic non-magnetic layer is replaced by an insulating layer. However, it was only in 1995, following advances in techniques for growing materials, that Jagadeesh Moodera and colleagues, and Terunobu Miyazaki and Nobuki Tezuka, were able to realize tunnel junctions with practical magnetoresistance. Further work by Parkin et al. and by Shinji Yuasa and colleagues, in 2004, proved that satisfactory room-temperature operation could be achieved when the barrier layer was made of magnesium oxide. The advance made in reducing the size of read and write heads has raised the hope that such spin-electronic effects might also be used for solid-state data storage. Indeed, the tunnel-junction structure is a useful template for such magnetoresistive random-access memory (MRAM) devices, as the two possible relative orientations of the magnetic layers could be interpreted as ‘bits’ in a storage device. Moreover, new concepts for devices are evolving continually (see also Milestone 20) — for example, S16 | March 2008 www.nature.com/milestones/spin © 2008 Nature Publishing Group in these systems. The origin of this ferromagnetism — and its potential use in spintronics devices — is still a matter of controversy, yet the search for a carrier-mediated room-temperature DMS continues. Fabio Pulizzi, Associate Editor, Nature Materials ORIGINAL RESEARCH PAPERS Von Molnar, S. & Methfessel, S. Giant negative magnetoresistance in ferromagnetic Eu1–xGdxSe. J. Appl. Phys. 38, 959–964 (1967) | Gałązka, R. R. in Proceedings of the 14th International Conference on the Physics of Semiconductors (ed. Wilson, B. L. H.) 133 (Institute of Physics, Bristol, 1978) | Munekata, H. et al. Diluted magnetic III–V semiconductors. Phys. Rev. Lett. 63, 1849–1852 (1989) | Ohno, H., Munekata, H., Penny, T., von Molnár, S. & Chang, L. L. Magnetotransport properties of p-type (In,Mn)As diluted magnetic III–IV semiconductors. Phys. Rev. Lett. 68, 2664–2667 (1992) | Ohno, H. et al. (Ga,Mn)As: a new ferromagnetic semiconductor based on GaAs Appl. Phys. Lett. 69, 363–365 (1996) | Dietl, T., Ohno, H., Matsukura, F., Cibert, J. & Ferrand, D. Zener model description of ferromagnetism in zinc- blende magnetic semiconductors. Science 287, 1019–1022 (2000) | Ohno, H. et al. Electric-field control of ferromagnetism. Nature 408, 944–946 (2000) fuRtHER REAdING Furdyna, J. K. & Kossut, J. (eds) Diluted Magnetic Semiconductors, Semiconductors and Semimetals Vol. 25 (Academic, London, 1988) By the late 1980s, magnetic resonance imaging (MRI; Milestone 15) had become a standard technique in hospitals and laboratories for the anatomical imaging of various tissues, from muscle to brain. However, MRI was only capable of revealing static structure and physiochemical information, but not actual function. The options for functional imaging were generally cumbersome, with low spatial resolution, and could require the injection of radioactive tracers into the bloodstream, as in positron emission tomography (PET), meaning that individual subjects could be scanned only infrequently. In 1990, however, Seiji Ogawa and colleagues published a series of breakthroughs that transformed MRI into a non-invasive and relatively inexpensive means of revealing physiological activity in the brain, sparking a revolution in the study of brain and behaviour. Ogawa et al. exploited two physiological phenomena that stemmed from observations made years earlier. First, in 1890, Charles Roy and Charles Sherrington had suggested that metabolic activity in the brain could be linked to vascular changes that would refresh blood supply. Later work established a more refined view: vasculature responds in an exquisitely localized fashion to bring oxygenated blood to areas of increased neural activity. This phenomenon was already being exploited in PET and other techniques. Second, Linus Pauling and Charles Coryell had reported, in 1936, that haemoglobin — the metalloprotein in red blood cells that acts as a major transporter of oxygen in humans and other species — has different magnetic properties in its oxygenated and deoxygenated forms. In three papers published in 1990, Ogawa and colleagues now showed how these two phenomena could be detected using MRI. First, they demonstrated that changes in the level of deoxygenated haemoglobin in blood changed the proton signal from the water molecules surrounding the vessels — an effect called blood- oxygenation-level-dependent (BOLD) contrast. Because metabolic activity in the brain involves changes in the relative levels of oxyhaemoglobin and deoxyhaemoglobin, Ogawa reasoned that it should be possible to track changes in brain activity by measuring the BOLD contrast — and in his third paper of 1990, he demonstrated exactly this. Manipulation of the brain metabolism and, hence, the blood oxygen of an anaesthetized rat — by adjusting anaesthesia or the composition of inhaled gas, or by inducing hypoglycaemia — led to changes in the BOLD contrast throughout the brain. Two years after this ground-breaking proof of principle, three independent groups (including that of Ogawa) published, almost simultaneously, demonstrations of task-related changes in the BOLD contrast in the human brain — proving not only that this method could be translated from anaesthetized animals to awake humans, but also that it could reveal localized brain function evoked by specific stimuli, such as visual images. BOLD-contrast imaging — or functional MRI (fMRI) as the technique is now commonly known — quickly became a mainstay of cognitive neuroscience. It is an accessible option for measuring brain activity with relatively high spatial resolution — resolution that has improved with advances in MRI hardware and techniques, and analysis methods. From the detailed characterization of the function of human visual brain areas to the discovery of areas that are potentially involved in higher cognitive functions, such as face recognition, empathy and self-awareness, the possibilities revealed by fMRI seem endless. I-han Chou, Senior Editor, Nature ORIGINAL RESEARCH PAPERS Roy, C. S. & Sherrington, C. S. On the regulation of the blood supply of the brain. J. Physiol. 11, 85−108 (1890) | Pauling, L. & Coryell, C. D. The magnetic properties and structure of hemoglobin, oxyhemoglobin and carbonmonoxyhemoglobin. Proc. Natl Acad.
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