621.317.4:535.33:539.

The Institution of Electrical Engineers Paper No. 4019 Nov. 1962

THE FIFTY-THIRD KELVIN LECTURE

'RADIOSPECTROSCOPY' By Professor B. BLEANEY, F.R.S.
{Lecture delivered before the INSTITUTION, 26th April, 1962.) Introduction
80r

The history of radio-spectroscopy begins in the 1920s with the experiments of Debye on solutions containing polar moleculesmolecules with permanent electric dipole moments. When an electric field is applied, a liquid containing such molecules acquires an electric polarization, since the equilibrium situation is one where a small fractional excess of the dipoles have their moments parallel to the field. This fractional excess is of order y*E\kT, where (JLE is the potential energy of the dipole (which favours alignment of a dipole /x parallel to the field E) and kT is the thermal energy of random motion (k being Boltzmann's constant and T the absolute temperature) which favours random orientation of the dipoles and thus opposes the alignment. When the electric field E is switched on or off, the polarization does not appear or disappear instantaneously since the dipoles are fixed in the molecules, which must therefore rotate to allow realignment of the dipoles. This rotation takes a finite time, its rate being regulated by the viscosity of the solution. The equilibrium situation is approached exponentially with a characteristic time, r, which is a time-constant like the r = RC which appears in the charging of a capacitance C through a resistance R. This analogy with a capacitance and resistance is rather close, since the solution behaves as an imperfect dielectric. The power dissipation is due to the work done in turning the molecules against the viscous forces in the liquid, and results in a heating of the solution. That part of the dielectric constant which is associated with rotation of the dipoles varies with frequency as (1 +jayf)~i, and is complex; the real part varies as (1 + (D2T2)~X, which has its full value only at low frequencies when the dipoles can reverse quickly enough to keep in step with the field, and falls to zero at very high frequencies when they cannot. The imaginary part varies as CUT/(1 + CO2T2), and has a maximum when CUT = 1. This maximum occurs because the losses are proportional both to the angle through which the dipoles turn in attempting to follow thefieldand to their angular velocity; the former decreases, but the latter increases, as the frequency of the alternating field goes up. As would be expected from the discussion, detection of the relaxation effect is accomplished by measurement of the electrical properties of the lossy capacitor formed byfillinga good capacitor with the liquid. To test the theory, measurements must be made over a range of frequencies such that cur varies from values small to large compared with unity. With the limited frequency range of radio equipment then available, Debye could achieve this only for substances such as the higher alcohols (e.g. glycerol), where the viscosity is high and the value of r comparatively long. For water at room temperature, r is about 10~ n sec and accurate measurements were made only after the war-time development of microwave equipment. Some results are shown in Fig. 1. A similar effect occurs in paramagnetic substances, which contain permanent magnetic dipoles of atomic origin; this was widely investigated by Gorter and other Dutch physicists in
Prof. Bleaney is Dr. Lee's Professor of Experimental Philosophy, University of Oxford.

Fig. 1.Real and imaginary parts of the dielectric constant of water as a function of frequency (reciprocal of the wavelength). the 1930s. Since atomic magnetic dipoles are of magnitude about 10~20e.m.u., while molecular electric dipoles are about 10~18e.s.u., the effects are rather more difficult to detect. In a solid the characteristic time, T, is determined by the rate at which the magnetic dipoles achieve thermal equilibrium with the lattice vibrations which form the reservoir of thermal energy. The coupling between the dipoles and the lattice varies widely, and so correspondingly does the relaxation time r (generally known as the 'spin-lattice relaxation time', since in many cases the magnetic dipoles are associated with the electron spin). However, at a low enough temperature the lattice vibrations will always die away sufficiently to bring the relaxation time into the millisecond region, long enough to make measurements possible using standard audio-frequency bridge techniques, the paramagnetic sample being placed in a coil to whose inductance and loss it makes a small contribution. (At radio frequencies difficulties arise from effects like dielectric loss, which, although coupled only to the stray capacitance of the coil, can be comparable in size.) The investigation of these two effects was carried out by methods very different from those of conventional spectroscopy, a point which has been characteristic of radiospectroscopy in general. We can endeavour to summarize the important features of radiospectroscopy as follows: (a) As in all spectroscopy, some mechanism must exist to provide an interaction between the substance and an electromagnetic field. In nearly all the cases of interest to us, this means the substance must contain either permanent electric or permanent magnetic dipoles of atomic magnitude. (b) The rate of spontaneous emission of radiation from atoms at radio frequencies is quite negligible. The spectra are therefore observed through interaction with a strong applied electromagneticfieldgenerated by an electronic oscillator. Such oscillators provide tunable sources which are virtually single frequency. For this reason no spectrometer of the conventional type is required to separate out radiations of different frequencies. (c) The degree of resolution which can be attained is usually determined, not by the resolving power of the spectrometer, but by the inherent width of the spectral lines themselves. In order

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BLEANEY: THE FIFTH-THIRD KELVIN LECTURE

that thermal equilibrium may be attained, some process must exist through which exchange of energy between the system of dipoles and the ordinary thermal molecular motion can take place. This process acts as a cause of damping in any forced oscillatory motion of the dipoles and results in broadening of the spectral lines. In the phenomena considered at the start of this lecture, the dipoles have no natural oscillatory frequency and their motion is determined by the relaxation processes; these are extreme cases where the line width is large compared with the frequency on which the line is centred. High resolution requires that the width be small compared with the natural resonance frequency. (d) Molecules with electric dipoles (atoms and nuclei do not have electric dipole moments) are firmly bound in solids and, as mentioned earlier, are subject to strong viscous forces in liquids. High-resolution spectroscopy is possible only with substances in an attenuated state, e.g. gases at low pressure. (e) Magnetic dipoles, which can interact only with magnetic fields, are relatively free, and high-resolution spectroscopy is possible in both solids and liquids, as well as gases. (/) All spectral lines in the radio-frequency region are extremely weak compared with those in the optical region. The problem, therefore, is to detect very small changes in the power reaching a receiver due to the presence of spectral lines, and spectrometers must be pushed to the limits of sensitivity. (g) With few exceptions, spectra observed at frequencies below 1000 Mc/s are due to nuclear magnetic dipoles; spectra due to electronic dipoles (electric or magnetic) are observed at centimetre wavelengths. Nuclear Magnetic Resonance using Molecular Beams Several important branches of radiospectroscopy involve magnetic dipole moments, and we shall consider first the nature of the motion of the dipole in a steady magnetic field and then the effect of an additional oscillatory field. In both the atom and the nucleus, permanent magnetic dipoles occur only in association with angular momentum, since they arise from the spinning motion (using spin in a rather loose way to include orbital motion) of an electric charge. A magnetic dipole therefore has the properties of a gyroscope, where the magnetic moment lies along the axis of the gyroscope. The motion in a steady magnetic field, which exerts a couple on the magnetic moment, is similar to that of an ordinary top in the earth's gravitational field (that is, under the action of the mechanical couple formed by the weight of the top acting through the centre of gravity and the equal and opposite reaction at the point of support). When the top is spinning rapidly about its own axis, this couple causes the axis to precess slowly about the vertical (the direction of the earth's gravitational field), a phenomenon with which we are all familiar as children. If damping is neglected, the precession continues indefinitely with the axis of the top at a fixed angle to the vertical. In the magnetic case the motion is similar. The magnetic moment, JX, bears a fixed ratio, y, to the intrinsic angular momentum, G: u = yG (1)

B-B, *-B,

(6) Fig. 2.Motion of atomic or nuclear magnetic dipole in the presence of steady and rotating magnetic fields.
(o) Precession of a magnetic moment |JI (associated with spin about its own axis) around a magnetic field B. (6) In a system of co-ordinates rotating in synchronism with a circularly polarized oscillatory field, B\, this field B\ is a constant vector. The apparent steady field is then B Bi, where Bi is the steady field at which the magnetic moment would precess in synchronism with B\. In this rotating system, the apparent motion of the magnetic moment is a simple precession about the resultant of the two fields By and B BL-

where y has the dimensions of (electric charge)/mass if the quantities are in electromagnetic units and is called the magnetogyric ratio. In a steadyfield,B, the angular velocity of precession (the so-called Larmor precession) is simply = yB
(2)

a result which is given by classical theory but is also correct in quantum mechanics. The negative sign indicates that, if y is negative (as for an electron with negative charge), the precession

is in the sense of a right-handed screw advancing along B, as in Fig. 2(a). Suppose we start with the magnetic dipole parallel to the steady field B and then apply an oscillatory magnetic field of small amplitude in the plane normal to B. This will have little effect unless its frequency coincides with the natural precession frequency of the dipole. A forced precession takes place in which the angle d between the dipole and the steady field B increases gradually from zero to a finite value, returns to zero and then increases again, repeating the cycle. The rate at which the angle 6 changes depends on the size of the oscillatory field (or, more precisely, on the size of its circularly polarized component B{ which rotates in synchronism with the natural precession); the maximum angle dm = 2a attained is given by tan a = Bxj(JB Bf), where B is the actual value of the steady field and BL is the value required to make the natural precession frequency coincide exactly with the applied frequency [see Fig. 2(6)]. Thus the maximum angle reached depends on how close the applied frequency is to the natural frequency; where they coincide exactly, the maximum angle is 180, i.e. the dipole can be completely reversed. This is a resonance phenomenon which occurs in such a striking fashion only when damping can be neglected. The magnetic moments of atoms were studied in the 1920s by the experiments of Stern and others, where the sideways deflection of a beam of atoms moving through an inhomogeneous magnetic field was observed. This field exerts a translational force which is proportional to the field gradient and the parallel component of the magnetic moment; the spatial quantization of angular momentum was demonstrated in this manner, but the accuracy with which magnetic moments could be determined was limited by the spread of molecular velocity in the beam, which means that different atoms spend varying times in traversing the inhomogeneous field and so suffer varying deflections. A natural extension of this method is to measure nuclear moments, but these are so much smaller (about 10~23e.m.u.) than electronic moments (about 10~20e.m.u.) that extreme difficulties are encountered. In the late 1930s, by a stroke of genius, Rabi conceived the idea of using the resonance phenomenon to reverse the orientation of a nuclear dipole in a known uniform magnetic field, B, and then to detect its reversal by the subsequent change in its path through an inhomogeneous field. In a molecular beam the atoms are quite free from collisions and the reversal of the dipole can occur as outlined above, provided that the ratio of the applied frequency to the steady

BLEANEY: THE FIFTY-THIRD KELVIN LECTURE

459

fields has made it simple to increase A/, the time required to traverse the space between them, and to decrease line widths so that measurements are readily made with an accuracy of DETECTOR about 1 kc/s in frequency; in special cases much higher accuracy has been attained. High-precision measurements on the hydrogen atom have greatly increased our understanding of atomic theory and have yielded much more precise values of several fundamental constants. Atoms which possess both electronic and nuclear magnetic Fig. 3.Principle of atomic beam magnetic resonance experiment. moments have been a special field of interest. Each of these Atoms (or molecules) from a source O are deviated downwards in the magnet A moments is acted on by the magnetic field of the other moment, through the translational force exerted by the inhomogeneous field of A on the nuclear magnetic moment. The atoms which then penetrate a slit S suffer a similar upwards and precesses about the direction of the total resultant angular deflection in the magnet B (whose gradient of field is in the reverse sense from that momentum, which is, of course, constant for a free atom not of A) and reach a detector. Magnet C produces a homogeneous field and in the region F a radio-frequency field (if at the right frequency) flips the nuclear moment subject to any external couple. The precession frequency is over; the atom then follows one of the paths indicated by broken lines and fails to reach the detector. characteristic of the atom; for hydrogen it is approximately 1420 Mc/s, a spectral line which is the basis of an important field is correct for resonance. This ratio gives the value of y, branch of radio-astronomy. The electron-nuclear interaction and hence the nuclear moment is found provided that the nuclear has provided detailed information about both atomic and nuclear spin (in units of h\2TT, where h is Planck's constant) is known structure for many isotopes; for highly radioactive isotopes from spectroscopic evidence. The apparatus devised for this (whose activity makes them easily detectable), atomic-beam purpose is shown in Fig. 3 and a typical resonance line is shown methods provide almost the only way of obtaining reliable in Fig. 4. The line width, Ato, is determined by the time, A/, values of spins and moments. A characteristic atomic frequency which can be measured MAGNETIC FIELD IN AMP/METRE with high precision forms the natural basis of an atomic fre1-5x105 1-6x105 quency standard which is free from the uncertainties of quartz I I I I clocks or the mean period of rotation of the earth. Stable 100 caesium atoms (isotope 137) are convenient for this purpose, since an atomic beam of low velocity can readily be obtained. Their characteristic frequency is approximately 9163 Mc/s and the precision of atomic clocks based on this spectral line has > \ improved steadily, notably through the work of Essen. A precision of about 1 part in 1011 can be obtained, which is i roughly a factor of 100 better than the reliability with which - 90 the mean period of the earth's rotation round the sun (the UJ astronomical unit of time) can be determined. At special radio HI stations the transmissions are now maintained within 1 part in 1010 of their nominal frequencies by checking against atomic \ clocks, and time signals are co-ordinated to 1 ms.

Microwave Gas Spectroscopy During the Second World War requirements for the accurate location of targets by radio led to the development of centimetreFig. 4.Drop in beam intensity reaching detector when magnetic field wave radar. Initially 10 cm, then 3 cm, and finally lcm of C is swept through the value required to make the nuclear wavelengths were developed. As the wavelength was decreased, precession frequency equal to the frequency of the radio-frequency scattering by raindrops (the magnitude of which depends on field. the behaviour of the complex dielectric constant of water in The resonance shown is for the 19 F nucleus in the molecule NaF, and the radio frequency is about 8 Mc/s at resonance. the anomalous Debye region) and absorption by the gases of the atmosphere became increasingly important. Much of the spent by the molecule in traversing the region occupied by the latter was due to the tails of absorption lines at still shorter oscillator field, since this limits the length of the wave train wavelengths; the work of Van Vleck and Weisskopf on the shape involved, and the product AcoAr is approximately unity. In of lines where the length of the wave-train is determined by the practice it is simpler to work at fixed frequency and to pass interval between molecular collisions was stimulated by the through resonance by varying the magnetic field, as in Fig. 4, need for more accurate estimates of the atmospheric absorption. where the line width appears in terms of magnetic field. In In this way the attention of physicists was drawn to the presence this way the nuclear moments of the proton, deuteron and a of molecular spectra at these wavelengths, while at the same number of other simple nuclei were determined to about one time, equipment (oscillators, detectors, waveguide components) part in a thousand. became available to open up a new region of the spectrum for Since 1945, the determination of nuclear moments of stable investigation. isotopes has been carried out more simply by nuclear magnetic A strong absorption band at about 1 cm wavelength in resonance in liquids or solids (as we shall see later), but beam ammonia gas was known from the pioneer work of Cleeton and methods have been fruitfully employed in other fields of radio- Williams in 1934. The NH 3 molecule has the form of a flat spectroscopy. These have used the electronic magnetic moments pyramid which vibrates between two equilibrium positions with of atoms which, being so much larger than nuclear moments, the plane of the hydrogen triangle respectively above and below give correspondingly larger deflections in inhomogeneous mag- the nitrogen atom. The vibrational frequency, about 24Gc/s, netic fields and make the whole technique much simpler. An is comparable with the collision frequency at atmospheric ingenious trick due to Ramsey using two separated oscillatory pressure and the absorption line is very broad. In 1945,
80

ISNR

1800

i i I 1900 2000 MAGNETIC FIELD IN E.M.U.

460

BLEANEY: THE FIFTY-THIRD KELVIN LECTURE

1 2

5SIO

Q -300
hv
0. K

hv

8
-200-

m
w,
NORMAL POPULATION INVERTED POPULATION REQUIRED FOR MASER ACTION

- 100

0-65

0-70

0-75 0-80 WAVENUMBER. CM"'

0-85

Fig. 6.Transition between two energy levels W\, Wi caused by quantum hv such that hv W% W\.
In thermal equilibrium, the population of the lower level is greater than that of the upper level, and more quanta are absorbed by raising molecules from W\ to W2 than are emitted by molecules jumping from Wi to W\. With an inverted population (more molecules in upper level) the net effect is changed from absorption to emission.

Fig. 5.Absorption spectrum of ammonia gas at a pressure of l-2mmHg.

The numbers above the absorption lines are the values of / , K; where J(hl2n) is the total angular momentum of the molecule and K determines the angle at which the axis of the molecule moves round the vector / .

Penrose and the author found that, on reducing the pressure to obtain smaller line width, a complex spectrum is observed (see Fig. 5). The vibrational frequency depends quite strongly on the flatness of the pyramid, and varies with the rotational state of the molecule because of centrifugal distortion. Discrete lines are obtained because the angular momentum of rotation is quantized; the two quantum numbers required to specify the state of rotation are shown above each line in Fig. 5. More resolution is obtained by lowering the pressure still further, and at about 0-01 mm Hg a hyperfine structure due to the electric quadrupole moment of the nitrogen nucleus was discovered by Good. The limiting line width is attained at a pressure where the molecular mean free path is of the order of the wavelength; the width due to collisions is then comparable with the width due to the Doppler effect, and is about one-millionth of the frequency of the spectral line. The discovery of hyperfine structure provided a further stimulus to the investigation of other spectra. These are mostly associated with molecular rotation, and can be observed if the molecular has a permanent electric dipole moment (or, in rare cases, a permanent magnetic moment, as in O2, which has an absorption band at wavelengths around 6 mm). As the angular momentum is quantized, observation of the frequency of rotation gives the moment of inertia of a molecule; observations with the same molecule containing isotopes of different mass then yield information about the inter-nuclear distances which is more accurate than can be obtained by other means. For example, in the linear molecule OCS, the oxygen-carbon and carbonsulphur distances are thus determined as 1-161 and 1-561 A, respectively. From hyperfine structure of such spectra much new nuclear information has been obtained. Splitting of the lines in magnetic and electric fields has also been studied; the latter gives a direct measurement of the size of the electric dipole moment of the molecule. As in all radiospectroscopy, the sensitivity of spectrometers has been pushed to the limit in the search for weak lines. In microwave spectroscopy the limit corresponds to an absorption of about 10% of the power in a path length of 1000 km. From a quantum mechanical viewpoint, any spectral line is the result of a transition between a pair of energy levels whose separation is equal to the quantum of radiation, hv. In the radio-frequency region this energy separation is always very small compared with the energy of molecular fluctuation, kT, where k is Boltzmann's constant. Since the population of a level with energy W is proportional to exp {WjkT), the difference in the numbers of molecules in two levels differing in energy by A W = hv < kT is approximately hv\kT under conditions of thermal equilibrium; for a wavelength of lcm and room temperature, the difference in population is about \%.

A beam of radiation (see Fig. 6) is equally effective in causing transitions from the lower to the upper level (stimulated absorption) as from the upper to the lower level (stimulated emission), and the net effect depends on the difference in the populations of the two levels. In thermal equilibrium the excess of population is in the lower level, and energy is absorbed by the molecules from the beam of radiation. (The smallness of the excess population in the lower state is one reason why radio-spectra are so weak). If by some trick an excess of molecules can be created in the excited state, they can be stimulated to emit radiation and feed power into a tuned circuit. This counteracts the damping through ordinary resistive losses, giving an effective negative resistance. If this is sufficient to outweigh the positive resistance of the circuit, spontaneous oscillation will occur at the natural frequency of the radiation. This exciting possibility was realized independently by Townes and Prokhorov in 1954. A beam of ammonia molecules passes through an inhomogeneous electric field, which produces a spatial separation of the molecules in the excited state from those in the ground state. The former then enter a highly tuned resonant cavity where stimulated emission occurs, and oscillation is set up provided that the beam is sufficiently intense. Estimated power outputs of 10~10W or more were obtained, with a long-term frequency stability of 1 part in 1010 and short-term stabilities of a few parts in 1012. The device can also be used as an amplifier, but it is untunable. As an oscillator it has been used to open up a new (but experimentally rather difficult) field of molecular spectroscopy, but its most far-reaching achievement has probably been to stimulate ideas. This is shown by the wide range of use of the word 'maser' coined by Townes as an acronym (Microwave Amplification by Stimulated Emission of Radiation) for the device, from which have followed words such as 'laser' for a parallel device (suggested by Townes and Schawlow) for light. At present the most promising device for the atomic frequency standard of the future is a maser essentially similar to the ammonia oscillator but based on the 1420 Mc/s line of atomic hydrogen. Since the rate of radiation from atomic magnetic dipoles is much less than from electric dipoles, the atoms must be stored in the cavity for correspondingly longer times. Fortunately this is possible because wall collisions have little influence on the magnetic dipoles of hydrogen atoms. A longer storage time gives the possibility of higher accuracy, and work at Harvard University under Ramsey envisages 1 part in 1013 in frequency precision. Nuclear Magnetic Resonance Detection of the precession of nuclear magnetic moments about an applied magnetic field in bulk matter was first accomplished in 1945. It is convenient to discuss the motion in terms

BLEANEY: THE FIFTY-THIRD KELVIN LECTURE

461

of the nuclear magnetization, the vector resultant of the individual nuclear dipole moments, which obeys the same equations of motion. In thermal equilibrium the magnetization is, of course, parallel to the steady magnetic field. If an oscillatory magnetic field is applied perpendicular to the steady field, the magnetization vector undergoes a forced precession about the steady field, but owing to relaxation effects, the precession is at an angle which is appreciably different from zero only at resonance and is negligibly small otherwise. This rotating component of magnetization can be detected in two ways: (a) It induces an oscillatory voltage in a pick-up coil, which is normally oriented at right-angles to the driving coil to avoid direct pick-up; this is the method of 'nuclear induction' invented by Bloch. (b) The transfer of power from the driving coil to the nuclei to replace that dissipated through the relaxation processes results in a damping of the coil, which can be observed by making it part of a tuned circuit; this is the method of 'nuclear magnetic resonance' due to Purcell. The additional damping is small compared with the natural resistive damping of the circuit, but it can be picked out by sweeping the steady magnetic field back and forward across the resonance value at a low frequency. The radio-frequency voltage across the coil is then modulated by the absorption at this low frequency, and the modulation voltage can be amplified after detection and displayed on an oscillograph (Fig. 7). A similar trick is used in nuclear induction.

Fig. 7.Absorption line due to nuclear magnetic resonance of protons in liquid water, displayed on oscillograph.
The vertical deflection is proportional to the strength of the absorption and the horizontal deflection to the variation in the applied magnetic field.

A limit to the degree of resolution attainable in magnetic resonance is set by the line width which arises from the damping effect of the spin-lattice relaxation, but in practice a much more serious limitation is set by interaction between the dipoles themselves ('spin-spin' interaction). Each dipole is subject not only to the external magnetic field but also to the fields of neighbouring dipoles; the latter vary in orientation, giving a spread

in the local field which amounts to a few gauss in a solid where most of the nuclei have dipole moments, such as proton-rich organic substances or simple inorganic fluorides. The effect is similar to that of inhomogeneity in the applied field, but where the nuclei are identical and precess at the same frequency, the effect is enhanced by a resonant coupling between them. In liquids, however, effects of this kind are averaged out by the rapid molecular motion. The precession frequency of a dipole will be displaced by the local field of a neighbour only if this field remains constant for a period greater than the duration of the wave train absorbed by the dipole from the applied oscillatory field. This condition is far from fulfilled in a liquid of low viscosity like water, where the Debye relaxation time of about 10~ n sec is a measure of the time for which a molecule remains fixed in orientation. Except in very viscous liquids, such as glycerol at low temperatures, the random local fields are averaged out very effectively, and resolution of the order of 1 part in 108 can be obtained. This requires very high homogeneity in the magnet used to supply the steady field; residual variation in field over the sample is averaged out by spinning the sample rapidly. As Purcell has said, the nucleus rides out these storms like a miniature gyroscope on perfect gymbals. The interest in such high resolution results from the fact that it is possible to observe the very tiny variation in magnetic field at different nuclear sites in a molecule. The local field differs from the external field because of the precession of the electron spins which gives rise to the normal diamagnetism; variation of the electron density from point to point within the molecule gives a corresponding variation in the local field. There are also interactions between different nuclear dipoles within the molecule which are not averaged out by the molecular motion. Both these effects are studied in order to elucidate details of chemical structure, and the fact that characteristic spectra are obtained from groups such as CH3 provides a further tool for the analytical chemist. Fig. 8 shows the nuclear magneticresonance spectrum of ethyl alcohol, where the three groups of lines belong to the protons in the OH, CH2 and CH3 groups, respectively. The separation between the groups is due to variation in the diamagnetic shielding at the different groups; thefinestructure within each group is due to spin-spin interaction between the protons. The spectrum was measured at 30 Mc/s (a magnetic field of about 7000e.m.u.), while the smaller splitings observed are less than 1 c/s. A relatively strong nuclear magnetic-resonance signal such as that of protons in water can be detected fairly easily; for example, by the decrease in the output of an oscillator whose level is marginal and therefore sensitive to the damping of its tuned circuit. The strength of magnetic fields which are reasonably homogeneous can be most easily measured accurately by proton magnetic resonance, since the only quantity to be determined is

AB

Fig. 8.Nuclear magnetic resonance spectrum at 30 Mc/s of ethyl alcohol.

Left, proton signal from OH; centre, proton signal from CH2 group; right, proton signal from CH3 group. The high resolution achieved is illustrated by the separation ofHnes A, B; this is about c/s.

462

BLEANEY: THE FIFTY-THIRD KELVIN LECTURE

solid. A large number of the main advances in thisfieldhave been due to my colleagues at the Clarendon Laboratory. The true nature of a number of point defects due to radiation damage has also been revealed, confirming or replacing earlier ideas which were little more than informed speculation. An important practical development from electron spin resonance is the solid-state maser, suggested by Bloembergen and realized experimentally (and independently) by Scovil. This makes use of paramagnetic salts which have at least three unequally spaced levels between which transitions can take place through the magnetic-resonance phenomenon. At low temperatures, where the energy separations are of order kT, the populations of the three levels are appreciably different, as shown in Fig. 11. If a strong microwave magnetic field is Electron Spin Magnetic Resonance applied at a resonant frequency, such as that corresponding to In substances which contain permanent magnetic dipoles the transition between levels A and C, transitions between this associated with electrons, magnetic resonance can readily be pair of levels can be induced at a rapid rate; transitions in either observed. The magnetogyric ratio of electrons is about a direction are equally probable, and if this were the only process, thousand times higher than that of nuclei, so that the precession the populations of the two levels would rapidly become equal. frequencies in fields of a few thousand e.m.u. correspond to This process is offset by relaxation effects which tend to restore wavelengths of a few centimetres, and the subject forms another the equilibrium ratios of the populations. At low temperatures branch of microwave spectroscopy. The increased size of the such relaxation processes are rather slow, and only a moderate dipoles means that local fields are correspondingly bigger, being power is needed from the oscillator to make the populations of several hundred e.m.u. for a typical paramagnetic salt. Line levels A and C nearly equal. As a result of this pumping widths are therefore of this order, an effect which can be over- action, the population of level C may exceed that of level B, come by 'diluting' the magnetic ions; that is, a substance such thus giving the possibility of maser action at the frequency as zinc-potassium sulphate is used, where rather less than 1 % corresponding to the separation of these two levels. In other of the diamagnetic zinc ions are replaced by paramagnetic copper ions. The residual line widths are then only a few e.m.u., owing to the nuclear moments of the protons in the water of crystallization. Coupling between the magnetic electrons and the thermal vibrations of the crystal lattice may also be strong, giving a very short spin-lattice relaxation time; this can be overcome by working at low temperatures, where the thermal vibrations have died out. This coupling is very variable, wellresolved spectra being observable at room temperatures in some salts, while in others cooling to liquid-helium temperatures (4 K) may be necessary. Fortunately, the large dipole moments also give high intensity, so that spectra can be observed from as few as 1012 ions. This makes it possible to observe spectra of magnetic centres formed by damage of the crystal lattice following exposure to ionizing radiation. Electron-spin resonance spectra are complex for a number of reasons. First, the motion of the magnetic electron is distorted by the electric fields of neighbouring ligands, and its magnetic behaviour is anisotropic; that is, the spectrum observed depends on the orientation of the applied magnetic field relative to the crystal axes. This makes it almost always essential to use single crystals. Second, hyperfine structure may be present owing to the nuclear magnetic dipole moment of the ion itself (see Fig. 10), or of the nuclei of neighbouring ions. The latter is enhanced when the binding is partially covalent, so that the magnetic electron is not localized on a single ion but is to some degree 'shared' between several ions. ConverFig. 9.Proton magnetometer. sely, the complexity of the spectra has This device gives an audible indication of the resulted in a wealth of information difference in proton magnetic resonance frequencies in two bottles of water, thus detecting local concerning the paramagnetic properties anomalies in the earth's field and eliminating effects due to diurnal variations or distant disof ions of the transition groups and the turbances such as d.c. electric traction. Field differences of 5 x 10~ 5 e.m.u. can be detected. nature of their chemical binding in a

the resonance frequency and frequencies can readily be measured with high accuracy using simple equipment. Even fields as small as the earth's field can be determined precisely by special, but not specially difficult, methods. In Oxford, the Research Laboratory for Archaeology and the History of Art has applied such techniques for the detection of buried pottery kilns, whose clay retains a permanent magnetic moment which causes an anomaly in the earth's magnetic field. Surprisingly, even filled-in pits and ditches can be located in this way, giving the archaeologists an invaluable tool for locating sites of possible interest without digging over vast areas, a costly and often unrewarding exercise. Fig. 9 shows a proton magnetometer in operation on a site.

BLEANEY: THE FIFTY-THIRD KELVIN LECTURE

463

, /

I,

Fig. 10.Electron paramagnetic resonance spectrum of silver atoms in KC1 at a frequency of 9354Mc/s.
The two widely separated bands show the splitting due to the nuclear magnetic moment of the silver nucleus, which can take up two orientations such that its field cither adds to or subtracts from the external field. The structure within each band is due to the magnetic fields of the magnetic moments of the six nearest chlorine nuclei. The spectrum shown is the derivative of the absorption signal.

words, if a small signal is applied at this frequency, it may be magnified by stimulated emission by the ions falling from level C to level B, which supplies power at the signal frequency in the right phase to make the signal grow. The importance of

STIMULATED EMISSION AT SIGNAL FREQUENCY

ABSORPTION AT PUMP FREQUENCY

POPULATION OF THREE LEVELS IN UNDISTURBED THERMAL EQUILIBRIUM

POPULATIONS UNDER PUMPING ACTION, SHOWING INVERSION OF RELATIVE POPULATION IN LEVELS B AND C

this as an amplifier is that its inherent noise corresponds to a temperature of a few degrees absolute, instead of several thousand degrees for the best type of electronic receiver. A low-noisetemperature receiver is invaluable in radio astronomy or satellite communication, where the aerial is directed at the open sky whose radiation background also corresponds to a low temperature. Conclusion It is, of course, impossible to do justice in a survey of this kind to all branches of radio-spectroscopy. For example, I have made no mention of ferromagnetic resonance, discovered by Griffiths in 1946, or similar electron-spin resonance phenomena in other substances where the spins act together in co-operative fashion under the action of exchange forces. Nuclear magnetic resonance has also played its part in such substances, acting as a probe to measure the internal magnetic field. Another important branch is cyclotron resonance, where the helical motion of a free charged particle in a magnetic field is detected by its interaction with an oscillatory electric field at the resonant frequency. With free electrons and protons, this has yielded the most accurate values at present available for the ratio of charge to mass for these fundamental particles. In semiconductors and metals, cyclotron resonance shows how the electronic motion in a magnetic field is modified through interaction with the periodic field of the lattice. A lecture which included reference to every important aspect of radiospectroscopy would be reduced to a mere catalogue. Instead, I have tried to give an outline of the chief lines along which the subject has developed, and to show how important practical applications have ultimately resulted. It should be emphasized that in every case the first steps in the various fields were taken as part of science of the purest kindfew aspects of physics could seem more remote from practical application than the determination of nuclear magnetic moments, but a direct descendant of this work is an atomic standard of frequency. An interesting feature of the history of radio-spectroscopy is that, by and large, the possibilities of practical applications have been realized by the same scientists as were responsible for the initial developments for 'pure' research work. Finally, the ideas which have come forward in radiospectroscopy have stimulated progress in other fields; I mention only the laser, suggested by Schawlow and Townes, in which coherent stimulated emission of light is produced, whose restricted spread in range of wavelength and angle of beam surpasses by orders of magnitude any previous achievements. Acknowledgments I am indebted to Dr. R. E. Richards, Physical Chemical Laboratory, Oxford, for Fig. 8, to Dr. M. J. Aitken, Research Laboratory of Archaeology and History of Art, Oxford, for Fig. 9 and to Dr. W. Hayes, Clarendon Laboratory, Oxford, for Fig. 10.

Fig. 11.Principle of three-level maser.

In thermal equilibrium the populations of the three levels decrease in ascending order of the energy. A strong microwave signal (the 'pump' signal) is applied between levels A and C, resulting in a greater population in level C than in level B. Maser action (amplification or oscillation) can then be obtained at the frequency corresponding to transitions between levels C and B.

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