Application of Submillimeter Wave Electron Spin Resonance J. Phys Soc. Jpan. Vol. 72 (2003) Suppl. B pp.

1225 c 2003 The Physical Society Japan

ESR Experiments on Quantum Spin Systems

Yoshitami Ajiro

Department of Physics, Kyushu University, Fukuoka 812-8581, Japan (Received February 3, 2003)

Our recent work is reviewed with focus on unique features of the application of Electron Spin Resonance(ESR) technique for quantum spin systems, together with a brief survey of historical backgrounds and recent progress in ESR and model systems. A example is presented in order to illustrate ESR powerfulness in view of high sensitivity, high energy resolution, and feasibility of high eld measurements by using pulsed magnetic elds. We apply the ESR technique to observe directly, for the rst time, quantum sine-Gordon excitations which have paramount importance in understanding unique quantum magnetism of the S=1/2 Heisenberg antiferromagnetic chain system, Cu-benzoate.
KEYWORDS: ESR, quantum spin chain, magnetic excitation, Cu-benzoate

1.

Introduction

Despite considerable eort, real experimental systems of quantum spins are still challenging objects in view of a stringent test for the peculiar features of simple yet nontrivial quantum systems. The Electron Spin Resonance(ESR) experiment in this research eld is rapidly growing. New compounds, which correspond to model systems previously considered, are discovered and new ESR techniques, which reveal novel situations of theoretical interest, are now developing, especially for multiple extreme environment such as high frequency, high magnetic eld, ultra low temperature, high pressure, and so on. The continuing eort in the development of ESR techniques towards higher eld and higher frequency is reecting the advantages for a broad variety of applications which can be gained from the increase in both these parameters. The present review is focused on representing a unique feature of the application of ESR technique for quantum spin systems. A typical example drawn from our recent work is represented in order to illustrate ESR powerfulness in view of high sensitivity, high energy resolution, and feasibility of high eld measurements combined with a pulsed magnetic eld. 2 is devoted to a brief survey of historical backgrounds and also recent progress in ESR and model systems. In 3, our recent work on the rst direct observation of quantum sine-Gordon excitations in the quantum antiferromagnetic chain system, Cu-benzoate is reviewed as an illustrative example of the advantage of high-frequency ESR technique, together with a brief survey of the related previous work. 2. ESR Experiments Model Systems and One-Dimensional

2.1 Historical backgrounds -old history up to 1980I would like to start this review with a brief historical survey of ESR and low-dimensional magnetism. As is well known, since the rst observation by Zavoisky(1945) and the subsequent observation by Cummerow and Halliday(1946), Electron Spin Reso

E-mail address: aji6scp@mbox.nc.kyushu-u.ac.jp 12

nance(ESR) technique has been applied initially to noninteracting paramagnetic substances, commonly referred to as Electron Paramagnetic Resonance(EPR). There followed an important and fruitful period(1950-1960) of EPR research at the Oxford group, in which much of our present-day understanding of the paramagnetic ions was established. The technique was immediately applied to ordered ferromagnets by Griths(1946) and Kittel(1947), referred to as Ferromagnetic Resonance(FMR) and antiferromagnets by Paulis et al. at Leiden(1953), referred to as Antiferromagnetic Resonance(AFMR). In view of the presence of strong exchange elds and magnetic anisotropy, both FMR and AFMR in the magnetically ordered phases are completely dierent from ordinary EPR. They represent a coherent precession of the entire magnetization or sublattice magnetization around the eective elds and are most characterized by a nonlinear dependence of the resonance frequency on the external eld, in contrast to EPR. AFMR technique was developed by Date in early 1960s to higher magnetic eld and applied to various systems including CoCl2 6H2 O and CoCl2 6D2 O. At the same time, there followed important theoretical development in AFMR, general ESR theory, critical ESR behaviors, and so on, especially by Japanese theorists, Nagamiya-Kanamori-Tachiki, KuboTomita, Mori-Kawasaki, and many others. Already at the early stage of long history, these experimental and theoretical pioneering studies engaged a fruitful future of ESR study on magnetic systems and they remain the most used still at present. Since then, it was widely recognized that ESR technique is a very powerful and useful tool to study the magnetic properties from a microscopic point of view. In the past, quite a lot of ESR studies have been devoted to various ordered magnets, in order to elucidate the magnetic interactions, magnetic ground states, collective motions of interacting spin systems, critical behaviors near the phase transitions, and so on. Among others, AFMR studies contributed to elucidate the spin wave branches of a variety of ordered antiferromagnets. The number of modes and the eld dependence of the resonance frequencies allow for discrimination between various spin arrangements.

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In the meantime, as early as 1958, experimental work on low-dimensional magnetism was started by Haseda et al. and was developed continuously in 1960s and 1970s, on a variety of one-dimensional(1D) model magnets such as Cu(NH3 )4 SO4 H2 O, CoCl2 2H2 O, Cu(C6 H5 COO)2 3H2 O(Cu-benzoate), CuCl2 2NC5 H5 (CPC), KCuF3 , (CH3 )4 NMnCl3 (TMMC), CsMnCl3 2H2 O (CMC), a family of hexagonal ABX3 such as CsNiF3 , CsNiCl3 , CsCoCl3 , and so on, and also a variety of 2D magnets such as Cu(HCOO)2 4H2 O, Mn(HCOO)2 2H2 O, K2 MF4 (M=Mn,Ni,Co,Cu), MnTiO3 , and so on. For details, see the review article by de Jongh and Miedema.1) It should be noted that these classic model substances still continue to provide us with rich physics in renewed interests. During these days, ESR technique was applied to a variety of low-dimensional spin systems which are characterized by well-developed short range order, neither in the paramagnetic state nor in the ordered state. The situation, of course, contains rich physics but often makes the interpretation of the experimental data somewhat dicult. As early as 1963, Date and Motokawa performed the ESR study on the ferromagnetic(FM) Isinglike chain, CoCl2 2H2 O2) and they observed unusual resonance modes, which can be characterized by neither EPR nor AFMR/FMR. They introduced a new concept of spin cluster resonance(SCR). This resonance corresponds to transitions between the Zeeman split states of thermally excited, localized spin clusters. The characteristic excitations of CoCl2 2H2 O were extensively studied as a function of an applied magnetic eld measuring the infra-red transmission by Torrence and Tinkham.3) These experiments are really the rst to demonstrate that ESR, especially in high-frequency, are powerful to probe unconventional elementary excitations of low-dimensional magnets which are not ordinary spin waves in the ordered magnets. About twenty years later the SCR concept was extended into antiferromagnetic(AFM) Ising-like chains. Elementary excitations of both FM and AFM Isinglike chains are not ordinary spin waves, but domain walls. We notice, however, an important dierence of the domain-wall dynamics between FM and AFM systems. The domain walls in FM chains are hard to propagate along the chains, resulting in the localized spin clusters which are the origin of SCR signals. On the other hand, those in AFM chains move easily due to the quantum mechanical eect of a small o-diagonal exchange interaction.4) ESR of AFM Ising-like chains was studied on CsCoCl3 .5, 6) The observed signal correspond to ESR transition between two states of the propagating domain walls. In terms of domain walls, the spin-cluster excitations are associated with a pair of domain walls. Since the excess energy per wall is |J| for S=1/2, the probabilities of thermally activated single domain wall and spin clusters are exp (|J|/kB T ) and exp (2J/kB T ), respectively, in agreement with the temperature dependence of signal intensity of the respective resonance. As for the Heisenberg systems, magnetic excitations in 1D systems have been a subject of intense study for a long time since Bethe(1931) and Hulthn(1938) studied e

the ground state of 1D S=1/2 Heisenberg AFM chains. For details, see the comprehensive survey by Mller et u al.7) and Mattis.8) In the ordered AFM, the magnetic excitations are the spin waves, the so-called magnons. However, the lowest excited states of 1D quantum spin chains are complicated by the fact that the exact ground state is not simply the ordered Nel state. At the inie tial stage, linear spin-wave theory was applied to the 1D Heisenberg AFM, assuming that the system in its ground state has staggered long-range order along the chains.9) This theory takes into account small deviations from the aligned Nel state, and the single spin e waves are transverse excitations (perpendicular to the staggered magnetization aligned along the z-axis due to the innitesimal anisotropy elds). It provides the wellknown dispersion relation, (q)=2JS|sin q| where J is the exchange constant of the Hamiltonian dened by Ji Si Si+1 . The contribution of the spin waves in the low temperature spin dynamics is reected in a peak at the spin wave frequency in the transverse structure functions Sxx (q, )=Syy (q, ). Inelastic neutron scattering studies on TMMC10) were in good agreement with the Anderson theory, and this was attributed to the fact that the eective spin S=5/2 of the manganese ion is suciently close to the classical limits S=. However, the limitations of the linear spin wave theory are intrinsically evident by a basic result that the symmetry-breaking Nel state is not a good approximae tion to the AFM ground state in 1D where the quantum uctuations are strongest. In 1962, des CloizeauxPeason(dCP) studied rstly quantum eects on the spectrum of the lowest excited states of the S=1/2 Heisenberg AFM chain based on Bethe ansatz technique combined with numerical calculation and found the spectrum obey the simple dispersion relation, (q)=(/2)J|sin q|, called as dCP spin wave. Quite surprisingly, it has the same dispersion as the Anderson spin wave apart from the fact that amplitude increases by a factor /2. Later investigations revealed that the lowest excited states are the triplet continuum with total spin S=1, whose lower boundary is given by the dCP spin wave whereas its upper boundary is given by (q)=J|sin(q/2)|. Faced with the discovery by Johnson and McCoy(1972) that the elementary excitations form the triplet continuum due to an internal degree of freedom in the magnon, Fadeev and Takhtajan(1981) ultimately reached the conclusion that this boson with S=1 properly is described as a composite particle consisting of two S=1/2 fermions. Later this constituent particle was named spinon by Anderson, in connection with high-TC superconductors with 2D antiferromagnetism. Experimentally, neutron scattering studies on S=1/2 Heisenberg AFM compound CPC,11, 12) revealed an asymmetrical line shape with a tail of spectral weight above a low-frequency cuto given by dCP excitations. However, a direct observation of the continuum in the entire momentum space remained up to 1990s because of lack of high energy neutron sources. Motivated by the experiments of neutron scattering in an applied magnetic eld on CPC12) and TMMC,13) the excitation spectrum of Heisenberg AFM chain in an applied magnetic eld was studied in late 1970s. For

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classical Heisenberg spins, the dispersion spectrum of the spin wave progressively distorts with increasing the eld until the critical eld is reached. For elds above the critical eld, the system changes to the FM phase with all spins aligned parallel to the eld and, hence, FM spin wave with the familiar cosinelike dispersion appears. In the extreme quantum limit (S=1/2) the situation is quite dierent. A transverse spin-wave dispersion curve for the quantum chain in nonzero eld was rst obtained by Pytte14) in 1974 based on the fermion representation and subsequently in 1977 by Ishimura and Shiba15) who used a Bethe ansatz technique. A comprehensive discussion of the longitudinal and the transverse spin dynamics of the S=1/2 Heisenberg AFM chain in a uniform magnetic eld and at low temperatures was provided in 1981 by Mller et al.7) In the presence of applied magnetic eld u H, the excitation spectrum undergoes drastic change. In view of intimate connection with our experiment, this topic is postponed until 3. As for the ESR experiment of the Heisenberg AFM chain, rather numerous ESR data were collected in the 1970s, for examples, the S=1/2 quantum AFM chain systems such as Cu-benzoate16, 17) and CPC,18) and also the S=5/2 classical AFM chain systems, such as TMMC19) and CMC.20) These experiments have revealed the anomalous behaviors of ESR in the 1D Heisenberg AFM systems. As for classical spins, especially for the case in which the anisotropy is dened mostly by the dipole-dipole and/or anisotropic exchange interactions, the experimental results were successfully interpreted in the framework of the Kubo-Tomita or Mori approach modied by the spin-diusion concept at high temperatures and also by the inclusion of short-range order eects at low temperatures: the anomalous angular dependences of the line shape and linewidth at high temperatures were explained by Richards in terms of characteristic diusional spin dynamics and also the peculiar temperature dependences of the linewidth and resonance eld at low temperatures were by Nagata and Tazuke in terms of the short-range order eect within a chain. However, for the S=1/2 systems with strong quantum uctuations, Nagata-Tazuke theory for classical systems cannot be fully adapted and, therefore, important open problems with respect to the peculiar behaviors of linewidth and the resonance shift were left, for a long time, without any unied interpretations for the quantum chains until recent systematic study of ESR in the quantum antiferromagnetic chain. Magnetic uctuations in low-dimensional magnetic systems have been studied in more extensive ways by means of neutron experiment. Neutron scattering can be used to scan entire momentum space, in contrast to ESR which probes only the excitations with the special momentum k=0 except some special cases. Besides the work mentioned above, other selected early examples of neutron experiments involve the pioneer work on CMC,21) TMMC for S=5/2 AFM chain,10) CsNiF3 for S=1 FM chain,22) and 2D AFM systems, K2 NiF4 ,23) Mn(HCOO)2 2H2 O,24) and K2 CoF4 .25) For details, see the review by Steiner et al.26) In the late 1970s and early 1980s, nonlinear magnetic

excitations were extensively studied by means of neutron scattering. Examples are the S= classical sine-Gordon solitons in CsNiF3 ,27) TMMC,28) and the propagating domain wall solitons in CsCoCl3 29) and in CsCoBr3 .30) It should be remarked that in these cases neutron scattering can not excite directly the nonlinear solitons but observe indirectly the eect on the line shape due to the collision of solitons. For soliton dynamics, see the review by Nagler et al.31) 2.2 Progress in experiments on model systems -after 1980The low-temperature properties of 1D quantum AFM have been of great interest for many years but particularly signicant progress has made in the last twenty years, in particular since Haldane made the prediction that integer-spin Heisenberg AFM chains should have a gap in the spin excitation spectrum, very dierently from half-odd-integer-spin chains without a spin gap.32, 33) Experimentally, neutron scattering34) and high-eld magnetization measurements35, 36) in S=1 AF chain, Ni(C2 H8 N2 )2 NO2 ClO4 (NENP) veried the existence of the Haldane gap as predicted. For the Haldane gap of integer-spin chains, see the review article by Aeck.37) This direct observation of spin gap in the Haldane system by high-eld magnetization measurements using pulse magnetic elds provided us with a break-through in experiment of new types of compounds which have quantum spin gaps. In addition, ESR experiment in this research eld has been steadily growing. New ESR techniques are now developing, especially for multiple extreme environment such as high frequency, high magnetic eld, ultra low temperature, high pressure, and so on. The continuing eort in the development of ESR techniques towards higher eld and higher frequency is reecting the advantages for a broad variety of applications which can be gained from the increase in both these parameters. Both experiments, magnetization and ESR measurements under pulsed high magnetic eld, are now stimulating many attempts to investigate a variety of quantum systems, particularly subjected to high magnetic elds, beyond the most simple case of the uniform chain with only one parameter of intrachain exchange constant between adjacent spins. Rather numerous experiments have revealed novel situations of quantum magnetism and stimulated theoretical interest. The modied chain systems include the nonuniform chains with spatial structures such as alternating linear chains including spin-Peierls system, spin ladders, frustrated spin chains with multiple competing interactions, and so on. These systems involve rich physics to be revealed for the highly nontrivial quantum phase transitions and also highly unconventional magnetization process with quantum magnetization plateaus. Spin gaps are found in many quantum spin systems. For example, ladder systems, quite remarkably, have a gap for an even number of legs and no gap for an odd number. This is reminiscent of the Haldane prediction. Examples include CuGeO3 for the spin-Peierls system,38) KCuCl3 for dimerised sys-

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tem,39) a series of Ni-complexs for S=1 alternating systems,40) Cu2 (C5 H12 N2 )2 Cl4 for the ladder system,41) (CH3 )2 CHNH3 CuCl3 for the alternating ferro- and antiferromagnetic bond chain,42) and so on. ESR studies on these spin-gapped substances were performed by KindoDate(1990),43) Lu et al.(1991),44) Palme et al.(1992),45) Brunel et al.(1992)46) for NENP, Palme et al.(1996)47) and Nojiri-Motokawa48) for CuGeO3 , Nojiri et al. for NaV2 O5 49) and NH4 CuCl3 ,50) Ohta-Motokawa(1999)51) for Cu2 (C5 H12 N2 )2 Cl4 and many others. Also, related research activities were revitalized by a discovery of high-TC superconductor by Bednorz and Mller in 1986 because the 2D quantum AFM describes u the parent compounds of the layered cuprate superconductors. In 1987, Anderson52) proposed the resonating valence bond(RVB) model for a possible mechanism of layered cuprate superconductors. In advance with this, Anderson53) suggested, in relation with spin-frustration eects on the triangular lattice, that a 2D fractional quantum spin liquid may take the form of a RVB state consisting of singlet spin pairing in the ground state, and with pairs of excited S=1/2 spinons separating via rearrangement of those singlet-bonds. The triangular lattice AFM were studied extensively in 1980s, especially in Japan by Mekata and Hirakawa for ABX3 compounds.54, 55) Nowadays, geometrically frustrated systems have attracted strong interest, primarily because they provide us with a possibility of observation of the spin liquid phases in 2D triangular and Kagom lattices and e even in 3D pyrochlore consisting of frustrated tetrahedra units.56) In frustrated quantum spin systems, the competition and/or interplay of quantum and frustration eects promises rich physics to be explored. In spite of extensive studies during the last decade, ground state properties of highly frustrated systems, particularly for high magnetic elds, are not fully understood yet and remains to be explored. Coldea et al.57) explored the ground state and dynamics of the 2D S=1/2 frustrated Heisenberg AFM, Cs2 CuCl4 using neutron scattering in high magnetic elds and concluded that this frustrated quantum AFM has a highly dispersive continuum of excited states, characteristic of RVB state, arising from pairs of spinons as in the S=1/2 quantum spin chain. In contrast, it was shown that the magnetic excitations in the unfrustrated 2D quantum AFM Cu(DCOO)2 4D2 O with a square lattice are well described by the magnon model based on a quantum renormalization of the classical system.58) Another example is the observation of nontrivial magnetization plateaus in the frustrated 2D quantum AFM SrCu2 (BO3 )2 .59) Nojiri and Motokawa revealed highly unusual features of magnetic excitations, localized magnons in a nite region of the lattice, of this interesting material by high-eld, high-frequency ESR.60) 2.3 Recent advance in ESR theory Finally, we mention recent advance of the ESR theory. Motivated by extensive ESR experiments, theoretical advancement directs forward mainly two directions. One is the ESR theory on the spin-gapped quantum magnets

such as Haldane systems. Experimentally, two types of ESR can be observed in spin-gapped systems. The rst type of ESR is the transition among the excited magnetic states. Another type of ESR is the transition from the ground state to the excited magnetic states. The latter type of ESR between the states with dierent total spins is usually forbidden because the total spin quantum number is not conserved, as known by the ESR selection rule for the mechanism of magnetic dipole transition. Moreover, the coupling between the probe rf magnetic eld and the ground state should vanish because the ground state is a pure spin-singlet when the system has no anisotropy. In order to compromise with this discrepancy, Sakai and coworkers6163) advanced the idea based on the mechanism in the presence of a non-secular term such as staggered eld and/or both static and dynamic Dzyaloshinsky-Moriya(DM) interactions, giving rise to the o-diagonal matrix element between the relevant energy states. In addition, in spin gapped-systems, when the external magnetic eld exceeds a critical value, it closes the gap and the system undergoes the quantum transition into a new gapless phase. The observed ESR spectra exhibit several peculiarities in the new phase. Theoretical eorts focus on the interpretation of these peculiarities and are now growing.64) Another direction concerns with the new approach to ESR in quantum spin chains from a eld-theory6569) and also from an exact numerical calculation.7072) Despite considerable eort, important problems of ESR in low-dimensional quantum magnets have been left since early 1970s, without any unied interpretation until recently, due to a clear lack of a comprehensive ESR theory, as far as low-dimensional quantum magnets are concerned. Very recently, Oshikawa and Aeck proposed a new theory for low-temperature ESR in half-integer spin AFM chains. The theory is based on eld theory using bosonization and the Feynman-Dyson self-energy formalism. They showed that the staggered DM interaction produces divergent behaviors of the linewidth proportional to H(H/T )2 and the shift of the resonance frequency proportional to (H/T )3 at low temperatures and applied to the old data of Cu-benzoate. Most importantly, they also showed that the second ESR, which corresponds to a sine-Gordon breather excitation, appears at very low temperature. This subject will be examined experimentally in detail in 3. More generally, the staggered DM interaction is one of the relevant perturbations responsible for the eldinduced spin gap formation in the critical quantum spin chain. These relevant perturbations produce the same divergent behaviors in ESR.69) On the other hand, irrelevant and marginal perturbations such as symmetric exchange anisotropy give the expression for the linewidth, including the eect of the large isotropic marginal operator, as H=(/J)2 [ln (J/T )]2 T . Such a linear temperature dependence of the width is observed approximately, over an intermediate range of temperature, in a variety of AFM chains, including the classic data of CPC18) and a series of data for KCuF3 ,73) CuGeO3 ,74) and NaV2 O3 .75) Further, Oshikawa and Aeck compared their eldtheory results with those of Kubo-Tomita theory for the

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high temperature regime. It was shown that a naive application of the standard Kubo-Tomita theory to the DM interaction gives an incorrect result. Miyashita and coworkers have developed a method for direct numerical calculation of the Kubo formula and studied ESR in S=1/2 spin systems. Using this method, they calculated the frequency dependence of the dynamical susceptibility for the nite number of spin systems and successfully reproduced the dynamical shift in a lowdimensional AFM model. This approach is very exible, naturally from a nature of method, and has been applied to study the linewidth and the resonance frequency as a function of temperature and magnetic eld in a variety of low-dimensional magnets. As for the high temperature ESR theory, the pioneering work of Kubo and Tomita, further developed by Mori, remains the most used at present. However, recent progress in ESR theory mentioned above paved the way to solve many puzzling features of ESR and has significantly improved our understanding of low-dimensional quantum systems. 3. Magnetic excitations in S=1/2 Heisenberg AFM chain

4 3

/J

2 1 0 q

Fig. 1. Sketch of the excitation spectrum of S=1/2 Heisenberg antiferromagnetic chain at zero eld.

Cu-benzoate,77) and Cu(C4 H4 N2 )(NO3 )2 (Cu-pyradine dinitrate)78) have established that the excitation spectrum is dominated by the gapless spinon continuum in the full brillouin zone as predicted, using neutrons from pulse spallation sources. 3.1.2 Eect of applied magnetic eld In the presence of applied magnetic eld, the excitation spectrum undergoes drastic change, quite dierently from the classical spin wave. For classical Heisenberg spins at zero eld, the ground state is of Nel type with e spins, say, parallel to the z-axis owing to an innitesimal anisotropy eld. The spin-wave excitations are then perpendicular to z, i.e., they contribute only to Sxx (q, ) and Syy (q, ). As soon as a very small eld is turned on, the classical AFM undergoes a transition to the spinop phase with spins essentially perpendicular to the eld. The rotational symmetry with respect to the zaxis is broken and the spins lie, for example, in the xz plane, also under an innitesimal anisotropy for the second preferred axis. Now, the spin waves predominantly contribute to Szz (q, ) and Syy (q, ). With increasing the eld until the critical eld is reached, the dispersion spectrum progressively distorts and develops a gap at q=0 for the transverse uctuations Syy and at q = for the longitudinal uctuations Szz , respectively. In the extreme quantum limit (S=1/2) the situation is quite dierent. At zero eld the ground state is a singlet. It is completely invariant under rotations in spin space. Hence, the longitudinal and transverse uctuations are equivalent. When a small eld is turned on, although the quantum system does not change to a spin-op phase, anomalies appear, nevertheless, due to the reduction of rotational symmetry, as shown in Fig. 2 where the longitudinal uctuations Szz (q, ) and the transverse uctuations Sxx (q, )=Syy (q, ) at T =0 in directions parallel and perpendicular to the applied eld, respectively, are represented. An important feature is that the ground state remains gapless up to the saturation eld. Besides the gapless excitations at q=0 and q=, the application of a magnetic eld develops new gapless excitations at the incommensurate wave-vectors qc =2m(H) and 2m(H). These wavevectors qc where the crit-

3.1 Introductory survey As mentioned already in 2, quantum antiferromagnetism in low dimensional systems has been a subject of intense study for a long time. While it is now well established theoretically and experimentally that AFM couplings(J) in one and two dimensions may give rise to very remarkable properties, in particular, at low temperatures(T J), real experimental systems of lowdimensional quantum spins are still challenging objects in view of a stringent test for the peculiar features of simple yet nontrivial quantum systems. Among them, the S=1/2 Heisenberg AFM chain with only one parameter of intrachain exchange constant is certainly the most simple one but involves rich physics to be revealed. 3.1.1 Spinon continuum In view of intimate connection with our experiment, I mention more about the unconventional excitations in the S=1/2 Heisenberg AFM chain. In our present knowledge, the system has a highly nontrivial ground state of critical state which is in the fractional quantum liquid state with no classical counterpart and also has the highly unconventional low-lying spin excitations. Unlike both conventional ordered magnets and gapped quantum spin chains which generally have sharp lowenergy modes identied with S=1 magnons, the elementary excitations in the S=1/2 Heisenberg AFM chain are so-called spinons in the modern language. Spinons can be visualized in terms of S=1/2 topological excitations identied with quantum domain walls between the two degenerate ground states, equivalent to quantum solitons. In the quantum liquid state, pairs of S=1/2 spinons are deconned from locally allowed S=1 states and, as a consequence of incoherent scattering of two particles, form the so-called spinon continuum, which is sketched in Fig. 1. Recent experiments on KCuF3 ,76)

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gBH/J=0.5

Szz Sxx(yy)

gBH 0 0 2m(H)

3.2.2 Quantum sine-Gordon model Dender et al. suggested that the gap might arise from the staggered magnetic eld generated by the alternating g-tensor, associated with the low symmetry of the crystal structure and the presence of two crystallographically inequivalent Cu sites on each chain of Cu-benzoate. It is rather well known from a general argument based on the crystal symmetry that the staggered eld, being perpendicular and proportional to the applied uniform eld, is produced by the staggered g-tensor and the Dzyaloshinsky-Moriya interaction in some crystal symmetry.83) Thus the Hamiltonian is given by H=J
i

/J

Fig. 2. Sketch of the lower edge of the excitation spectrum of S=1/2 Heisenberg antiferromagnetic chain in the presence of external eld, gB H/J=0.5.

Si Si+1 + H
i

z Si + h i

x (1)i Si ,

(1)

where H represents the applied uniform eld and h the staggered eld proportional to the applied magnetic eld ical zero-energy uctuations take place are shifted con- H, hence h=cH. Based on a eld theory approach, tinuously in proportion to the magnetization m(H) with a description was then proposed by Oshikawa and Afremaining no energy gap as the eld increases; dynam- eck(OA)84, 85) and, subsequently by Essler and Tsveical incommensurability. In particular we see that the lik(ET).86, 87) They proposed that the observed eldlongitudinal Szz (q, ) has the soft wave-vectors 0 and induced gap is caused by an eective transverse staggered 2m(H) whereas the transverse Sxx (q, )=Syy (q, ), magnetic eld imposed on alternate spins in chains, and has the soft wave-vectors and 2m(H). These fea- showed that the induced gap has a dependence H 2/3 tures are in totally contrast with classical chains. The on the applied eld H in agreement with the experirst experimental verication of the eld-dependent dy- ments. Most interestingly, as was shown theoretically, namical incommensurability was provided very recently the S=1/2 AFM Heisenberg chain system subjected to the transverse staggered eld is mapped to the wellin Cu-benzoate by Dender et al.79) known quantum sine-Gordon(SG) model on the basis of a low energy eective eld theory. The model was studied 3.2 Magnetic Excitations in Cu-Benzoate intensively in the past and various properties are known 3.2.1 Field-induced gap Recently, Dender et al. performed a series of experi- because of its exact integrability. The spectrum of the ments on deuterated Cu-benzoate, Cu(C6 D5 COO)2 3D2 O, low energy SG excitations consists of a soliton-antisoliton 77, 79) the well-known S=1/2 Heisenberg AFM chain with doublet with mass M and their bound states which are an exchange coupling J/kB =17.2 K in the Hamiltonian called breathers. For Cu-benzoate the soliton mass as Ji Si Si+1 .80) In a neutron scattering experiment at a function of the applied magnetic eld was determined zero eld, they obtained clear evidence of a continuum by OA, 2 of magnetic excitations, consistent with the current the(2) M 1.85J(h/J )1/(2 /4) , oretical picture of the spinon excitation spectrum with the dCP lower bound for the S=1/2 chain at T =0 K. where is the eld-dependent coupling constant in the Moreover, under magnetic elds, they provided the rst model and h the staggered eld. Using 2 =2 at zero direct experimental evidence for the eld-dependent in- eld, we obtain the eld dependence of mass M which commensurate low-energy modes of spinon excitations: is in good agreement with the observed eld-induced ennew low-energy modes appear at the eld-dependent in- ergy gap Eg (H) as a function of external magnetic eld; commensurate wave vectors qc in agreement with the M =Eg (H)H 2/3 . prediction. Most importantly, however, they discovered, In addition, for the quantum SG, there are quantized at the same time, that the modes are not completely breathers denoted by B1 , B2 , , with discrete masses soft in contradiction to the prediction for S=1/2 Heisen- Mn given by berg AFM chain system. Furthermore, the specic heat (3) Mn = 2M sin(n/2); n = 1, 2, , [1/], measurements under magnetic elds revealed an unusual eld-induced energy gap Eg (H) which seemed to scale as 2 2 approximately H 2/3 . It should be noted that no 3D mag- where = /(8 )=1/3 at H=0. Then, the mass of netic ordering is found down to 20 mK from our recent quantized breathers are approximately given by M1 =M , SR experiment81) and thus the observed features should M2 = 3M , M3 =2M , and so on. ET calculated the be attributed purely to the 1D character of the system. mass spectrum as a function of magnetic eld for CuMore recently, Karaki et al. found some indication of 3D benzoate and they found that for small elds there are magnetic ordering around 1 mK from the susceptibility three breathers, one of which is just below the solitonantisoliton continuum starting at 2M . For higher elds measurements.82) further breathers split o this continuum. In the presence of H, the triplet at the zero eld is now split, with

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the lowest breather having a smaller mass than the degenerate soliton-antisoliton doublet. OA carefully examined the contribution to the excitation spectrum. They showed that the soliton and antisoliton are created by the qc =2m(H) component of Sz and the odd- and even-numbered breathers by the q= component of Sy and Sx , respectively. Thus the odd and even breathers contribute respectively to the single particle excitation in Syy and Sxx while the soliton and antisoliton to the single particle excitation in Szz . By calculating the dynamical magnetic susceptibilities, ET and OA independently have suggested that some of the observed peaks of inelastic neutron-scattering experiments can be identied with the SG excitations, though the assignment is not conclusive yet. It is interesting to note that the sine-Gordon solitoms and breathers are fundamentally dierent from the spinons of the S=1/2 chain. Shiba et al.88) also studied magnetic excitation spectrum S(q, ) in the presence of both staggered and uniform magnetic eld, from a quite dierent approach, using the exact-diagonalization method for nite chain. The results clearly show, for both longitudinal and transverse uctuations, the reminiscent of the incommensurate eld-dependent soft mode for S=1/2 AFM Heisenberg chain without staggered eld and also, at the same time, show the eld-induced energy gap as the local minimum of energy spectrum due to the eect of the staggered magnetic eld. These features are in good agreement with the neutron-scattering data for Cu-benzoate. Another important feature of the calculated spectrum is that the lowest branch is isolated and above this branch a continuum exists. In view of the fact that Cu benzoate is the rst candidate for experimental realization of the quantum SGmodel, it is of particular importance to observe these SG excitations more evidently in order to give a stringent verication for this fascinating model. For this purpose, ESR is a particularly sensitive technique to probe low-energy, long-wavelength excitations and provides the most unique and powerful technique because of various advantages such as high sensitivity, high energy resolution, and feasibility of high eld measurements by using pulsed magnetic elds. 3.3 ESR Study of Sine-Gordon Excitations in Copper Benzoate Here, we apply a high-frequency and high-eld ESR technique to perform the rst direct observation of the characteristic excitations of a fully quantum SG system, particularly to investigate the behaviors in a wide range of magnetic eld up to H2J.89, 90) Measurements have been performed on single crystals of Cu-benzoate at low temperature down to 0.5 K, using a vector network analyzer in the frequency region between 53 and 109 GHz and a superconducting magnet up to 18 T and conventional Gunn oscillators and optical pumped far-infrared laser for radiation sources up to 650 GHz, combined with pulsed magnetic elds up to 30 T. We performed two types of measurements with dierent polarization of rf-eld, namely the usual ESR condition(HHrf ) re-

(a) 190 GHz B S Transmission (arb. units)

0.5 K 1.0 1.6 2.0 3.0 4.2 6.0 8.0 10 20

(b) 428.9 GHz 0.5 K B 1.6 2.0 3.0 S 4.2 6.0 8.0 10 20

5.0

5.5 H (T)

6.0

6.5 12.0 12.5 13.0 13.5 14.0 14.5 H (T)

Fig. 3. Examples of ESR spectra at 190 GHz and 428.9 GHz for H c in the Faraday conguration. The symbols, S and B, represent spinon signal and breather signal, respectively.

ferred to as Faraday conguration and the parallel pumping condition(H Hrf ) referred to as Voigt conguration. These measurements allow us to probe either the perpendicular component of uctuations Sxx(yy) or the parallel component of uctuations Szz with respect to the applied eld, respectively. Based on the SG model, it is shown that the odd- and even-breathers contribute respectively to the single particle excitation in Syy and Sxx while the soliton and the antisoliton to the single particle excitation in Szz . Thus, we naively expect that the respective ESR intensity under the Faraday and the Voigt conguration is dominated by the breather modes and the soliton/antisoliton modes. Indeed, based on the SG model, Oshikawa and Aeck have shown that the ESR intensity under the Faraday conguration is dominated by the breather mode and reanalyzed the previous ESR data at low temperature observed by Oshima et al.17) in terms of the newly proposed breather excitation.65) As will be shown below, we succeeded, for the rst time, in probing the transverse uctuations Sxx and Syy at q=0 under the Faraday conguration and also the longitudinal uctuations Szz at q=0 under Voigt conguration in the wide eld and temperature ranges by using the advanced technique of high frequency ESR. The results clearly show that the predicted low-energy quantum SG excitations are now experimentally proved to exist in the real system, Cu-benzoate. 3.3.1 Faraday conguration Figure 3 shows a rather unusual behavior of ESR spectra for H c under Faraday conguration as a function of temperature for two frequencies. We can easily designate the three temperature regions in which ESR spectra behaves quite dierently; a high-T regime (named spinon regime), an intermediate-T regime (crossover regime) and a low-T regime (breather regime). As is seen, the signal S shifts to the lower eld side with decreasing tem-

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19

525.8 GHz

0.15

428.9

(T)

0.10 95 GHz 135 190 326.1 428.9 525.8 0 1 2 (H/T)3 [T3K-3] 3

H (T)

0 190

0.05

0.00

0 135 0

Fig. 5. The scaling plot of the resonance eld shift.

0.5

1 T (K)

10

20
anomaly of the old data for Cu-benzoate.17) Now we apply this theory to the present data in the rather wide eld and temperature ranges. Actually, both the temperature and eld dependences of the linewidth of the signal S at dierent frequencies are well reproduced by the dominant functional form (H/T )2 predicted by OA for the staggered-eld eects, as shown by the solid curves in Fig. 4. In the tting, a small H term was included. It should be noted that the data at all frequencies are satisfactorily reproduced, except in the vicinity of the crossover regime, with only two parameters, =0.087[K2 T1 ] and =0.007, in the wide temperature and eld ranges. In addition, the shift of the resonance eld also follows the predicted functional form (H/T )3 , as shown in Fig. 5. The slope of the plot is linear below (H/T )3 1, showing the validity of scaling as (H/T )3 . The deviation above (H/T )3 1 is naturally explained since the pure spinon picture breaks down in this regime. In view of overall agreement with the predicted behaviors in the high-T regime, the signal S can be identied as a spinon resonance. Hence, the high-T regime is named the spinon regime. (b) breather regime In the low-T regime, on the other hand, a new signal B appears in the low eld side. The linewidth of signal B very steeply decreases as T is lowered below the crossover regime, in high contrast with the case of the signal S. As represented by the dashed lines in Fig. 4, temperature dependence is featured well by the formula, exp [Eg (H)/T ], suggesting a thermal activation process with the excitation gap Eg (H). It should be noted that Eg (H) is not an adjustable parameter but is the experimentally observable quantity from the resonance elds, as shown later. It is natural to consider that the linewidth may be determined from a concomitant lifetime (or nite free path) due to collision depending on the number of excited particles. In their recent theory on ESR, Oshikawa and Aeck(OA) have also shown that the second ESR, which corresponds to a SG breather excitation, appears at very low temperature. The qualitative behaviors of the signal B are in accord with the breather picture by OA. Hence, the signal B can be identied as the second ESR, which corresponds to a SG

Fig. 4. The temperature dependence of the line width for the spinon signal (solid circles) and the breather signal (solid triangles). The solid and the dashed lines represent the theoretical dependences.

peratures when T J, accompanied with the rapid broadening of the line width. As the temperature is decreased further, a novel signal-crossover happens as indicated by a double-peak structure and, nally, a new signal B appears in the low eld side at the lowest temperature. To examine the nature of this crossover, we decomposed each spectrum into two Lorentzian lines, S and B. The derived linewidths as a function of temperature are plotted in log T -scale in Fig. 4. (a) spinon regime The width of the signal S increases continuously with decreasing temperatures. For an Heisenberg AFM chain, a gapless spinon excitation develops due to the shortrange correlation within the spin chains when a temperature is much lower than J. At this point, it is worth noting that the q=0 spinon mode in Sxx =Syy is shifted in energy by a quantity equal to the Zeeman energy gB H, while the energy of Szz remains zero. In this high-T regime, ESR signal is nothing but the q=0 mode of the spinon continuum in the transverse uctuations, say, Sxx . From this view, ESR in the S=1/2 antiferromagnetic Heisenberg chain at low temperatures is worth being called Spinon Resonance.91) At T =0, a sharp ESR signal would be observed at Zeeman frequency if there were not any anisotropies, because q=0 spinon continuum has zero width. Recently, Oshikawa and Aeck(OA) have developed a eld-theory approach to ESR on quantum spin chains at low temperature and shown that a drastic broadening of the ESR linewidth is caused by a staggered eld due to development of the correlation length. According to the theory, the staggered DM interaction produces divergent behaviors of the linewidth proportional to H(H/T )2 and the shift of the resonance frequency proportional to (H/T )3 at low temperatures. The theory can explain the ESR

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Transmission (arb. units)

20

400 350

T B3

15 H (T)

B2 DPPH

300 250

190 GHz
BT 1 2 3 4 5 H (T) 6 7

H // c H // c" H // a H // b

10

Eg (GHz)
0 2 4 6 8 T (K) 10 12

200 150 100 50

10 H (T)

15

20

25

Fig. 6. Sketch of the dynamical crossover region in the temperature-eld diagram. The symbols (solid square and solid diamond) represent the onset of the deviation from the formulas for the spinon regime in the linewidth and in the shift, respectively. The thick horizontal bars represent the signal coexisting region. The solid line is an eye guide. The dashed line is the curve of kB T =Eg (H)

Fig. 7. The eld dependence of the SG excitation gap Eg (H) for dierent eld orientations, determined from the main signal BT 1 in the Faraday conguration, using eq.(4). Open circles show the result from specic-heat measurements. The solid and the dashed lines are the theoretical curves of Eg (H) = cH 2/3 for respective orientation of the magnetic eld. The inset shows the typical example of the ESR spectrum in a wide eld range, observed at 190 GHz and at 0.5 K for H c in the Faraday conguration. Higher order signals are clearly observed.

breather excitation in the eld-induced gapped phase, and the low-T regime is named the breather regime. (c) cross-over regime The signals S and B coexist in some temperature region, and, in this crossover regime, the spectral weight shifts gradually from the signal S to the signal B by keeping the total intensity constant. Of particular interest is that the crossover region depends on the frequency and, consequently, on the eld, and shifts to high temperatures with increasing frequencies, as easily seen from the typical spectrum at 190 GHz and 428.9 GHz in Fig. 3, and also from Fig. 4. In Fig. 6, the onset temperatures where the shift and the linewidth start to deviate from the proposed functions are plotted for different frequencies. The coexisting regime for the S and B signals is represented by thick horizontal bars. It is instructive to point out that the crossover appears when the temperature is comparable to the eld-induced gap and the anomalous region in ESR is spreaded over the curve kB T =Eg (H) due to thermal eect as indicated by a hatched area in the inset. Since the magnitude of the energy gap changes as Eg (H)H 2/3 , this crossover temperature is also expected to behave as Tc (H)H 2/3 , indicating that the critical point is located at T =0 and H=0. This nding clearly indicates that the crossover regime designates the boundary between the gapless high T -low H state (Eg (H)/T <1) and the gapped low T high H state (Eg (H)/T >1). The drastic change of the ESR spectra is usually considered to be an indication of onset of the 3D ordering but it is not the case for Cu-benzoate. Since the linewidth, as well as the shift, probes the essential dierence of the spin uctuation spectrum between two regimes with and without an energy gap, it is convincing that the observed anomaly of the ESR signal is the manifestation of the spinon-breather crossover. In my sense this crossover phenomenon is a direct consequence of the fact that a common relevant perturbation, more specically the staggered eld, is responsible for the divergent behaviors in ESR in the spinon regime and also for the eld-induced gap formation in the breather regime. It should be stressed that such a dynamical crossover was observed here for the rst time directly by means of ESR technique. The ESR anomaly can be explained in terms of the dynamical crossover between the gapless spinon regime and the gapped breather regime. (d) breather mode In order to conrm that the signal B is certainly the breather mode, we examined the frequency-eld dependence of the signal B at 0.5 K for dierent eld orientations. The resonance eld shifts to the low eld side from the conventional Zeeman mode and its frequencyeld curve exhibits the nonlinear eld dependence. As is supposed from the spinon mode in Fig. 2, it is quite natural to consider that, in addition to the Zeeman energy gap gB H, the breather mode at q=0 in the transverse uctuations has a simultaneous contribution from the eld-induced gap Eg (H) at qc due to the staggered eld. In consequence of superposition of two energy gaps at q=0 and qc , the ESR frequency-eld relation in the Faraday conguration is given, as predicted OA, by (h)Faraday = (gB H)2 + Eg (H)2 , (4)

where and g are the frequency of ESR and the g-value, respectively. The equation means that a nonlinear frequency-eld relation is caused by the presence of Eg (H), magnitude of which depends on the eld intensity as well as the eld orientation. From this relation, we can estimate

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21

T = 0.5 K T B1 BT
2

BL 108.45 GHz
1 2

97.84 GHz S E Transmission (arb. units)

BL

105.00 103.06 97.84 71.85 68.91 57.62

BT 1 0 2 4
L B1

3.8 K 3.2 2.3 1.8 1.2 1.0 0.8

Transimission (arb. units)

BL BT 2 2

0.5

6 8 H (T)

10

12

14

6 8 H (T)

10

12

14

Fig. 8. Typical ESR spectra for H c in the Voigt conguration for various frequencies at T =0.5 K.

Fig. 9. Typical ESR spectra for H c in the Voigt conguration for various temperatures at 97.84 GHz.

the Eg (H) straightforwardly by putting the experimental values of and H, as well as g values, ga =2.20, gb =2.06, gc =2.25 or gc =2.29 determined at suciently high temperature. The determined energy gap Eg (H) as a function of magnetic eld is shown in Fig. 7, together with the predicted eld dependence H 2/3 . It should be noted that in the whole analyses we did not use any free parameters but only the experimentally derived values, including the prefactor of the eld dependence. Now it is evident that the signal B is identied with the predicted rst breather mode, which is now redesigned BT where 1 the sux T stands for transverse mode. In Fig. 7, Eg (H) is large for H c and H c, and small for H a and H b, in accordance with the angular dependence of the eld-induced gap. For H a and H b, the induced gap is not large enough to satisfy the condition as kB T Eg (H) even at 0.5 K. In fact, a small gap for H b was successfully observed from the measurements at 220 mK using a 3 He-4 He dilution refrigerator.92) 3.3.2 Voigt conguration Typical ESR spectra for H c in the Voigt conguration are shown in Fig. 8 for various frequencies at T =0.5 K and in Fig. 9 for various temperatures at 97.84 GHz. Each spectrum is composed of several distinct lines: one is a main signal BL at higher eld, where the suf1 x L stands for longitudinal mode corresponding to the uctuations Szz , and a series of weak signals which are discussed below in (c). Based on the argument by OA that the soliton and the antisoliton contribute to the single particle excitation in Szz , we naively expect that the ESR intensity under the Voigt conguration is dominated by the soliton/antisoliton modes since the ESR

response corresponds to Szz in this conguration. (a) soliton/antisoliton mode For the q=0 spinon mode in the longitudinal uctuations Szz , there exists no energy gap irrespective of presence of the magnetic eld as seen in Fig. 2, in contrast with the transverse mode which has a Zeeman energy gap gB H. Therefore, it is natural to expect that the longitudinal mode at q=0 in the present case may exhibit directly the eld-induced gap Eg (H) due to the staggered eld. Then, the ESR frequency-eld relation in the Voigt conguration is given by, (h)Voigt = Eg (H), (5)

This equation has outstanding signicance to be noticed that the eld-induced gap is determined directly and precisely from the resonance frequency as a function of applied magnetic eld, without any analysis in contrast with eq.(4) in the Faraday conguration. The frequency-eld relation of the main signal BL and, 1 consequently, the eld dependence of the eld-induced gap, is shown in Fig. 10, together with the energy gap derived from the BT data (see Fig. 7) and the expected 1 behavior of Eg (H). The solid line is the theoretical curve of Eg (H)H 2/3 with the same prefactor as in Fig. 7. We notice two remarkable features. One is that the eldinduced energy gaps which were either directly determined from the BL data using eq.(5) or indirectly from 1 the BT data using eq.(4) are mutually consistent with 1 each other. The second is that the calculated curve reproduces well the experimental data below about 10 T but apparently deviates at high-eld region. As concerns the rst point, a remark should be made.

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200 BL
1

150 Eg (GHz)

BT 1

100

50

10 H (T)

15

20

Fig. 10. The eld dependence of the SG excitation gap Eg (H) for H c. Solid circles represent the soliton/antisoliton energy gap determined from the main signal BL in the Voigt conguration, 1 using eq.(5). Open circles represent the breather energy gap determined from the main signal BT in the Faraday congu1 ration, using eq.(4). The solid line is the theoretical curve of 2/3 . Eg (H) = cH

In the Faraday conguration we identied the BT signal 1 with the rst breather mode. If we naively identify the BL signal with the soliton/antisoliton mode, the masses 1 of two modes are expected to be equal at zero eld but not equal at nite eld where the triplet is now split, with the lowest breather having a dierent mass than the degenerate soliton-antisoliton doublet. This interesting point should be claried in future. (b) high-eld correction It is worth discussing the origin of deviation since the experimentally determined Eg (H), especially from BL , is 1 quite accurate. The obvious deviation may arise partly from neglection of the eld dependence of the coupling constant and more seriously from breaking of the quantum SG model beyond applicability. In fact, ET calculated as a function of the applied eld and showed that 2 =2 at zero is getting smaller with increasing eld and nally reaches 2 = at a critical eld (H=2J=27 T) into the saturated FM state. This causes a gradual change of the exponent p of the eld-induced gap, Eg (H)H p from p=2/3 at lower elds to p=4/7 at higher elds. The feature explains partly the observed deviation at high-eld region. 3.3.3 Higher-order excitations The inset of Fig.7 shows a typical spectrum taken at 190 GHz and at 0.5 K for H c in a wide eld range with the Faraday conguration. Besides the strongest main signal, which corresponds to the rst breather signal BT 1 mentioned above, weak but denite signals BT and BT 2 3 are visible when the external eld is extended to the lower elds. The eld dependence of the resonance elds of BT and BT behave as hierarchical satellite signals of 2 3 BT , suggesting that the possible origin of these satellite 1

signals is due to the higher breather excitations. Figure 9 shows a typical spectrum taken at 97.84 GHz for various temperatures with H c in a wide eld range and in the Voigt conguration. Besides the strongest main signal BL mentioned above, a series of weak sig1 nals, now assigned as BL , BT , and BT , come in order 2 1 2 at low eld side. The mixture of signals BL and BT is due to intended misalignment of the sample to polarization vector of the probe rf-eld, which is assured from a good coincidence between data in two congurations with respect to the resonance eld as well as the relative intensity of BT and BT signals. It is of interest to 1 2 note that the polarization dependence is apparent for BT and BL and the features of transverse and longitudinal uctuations are quite dierent in their resonance conditions such as resonance elds and linewidths. These features were employed for identication of BT and BL n n signal in the above. The intensities of all these signals increase with decreasing temperature, indicating that these signals correspond to ESR transitions from the ground state. Besides, in Fig. 9, we notice a curious signal E around 10 T. This signal can be observed only in the restricted temperature region. The temperature dependence of the signal intensity apparently shows that the signal E corresponds to ESR transition between excited states. The useful hints for possible origins of these higherorder excitations such as BT , BT , BL , and E are provided 2 3 2 by examination of magnetic excitation spectrum S(q, ) in a magnetic eld. ET calculated the transverse uctuations, Sxx (q, ) and Syy (q, ) near q= at several specic magnetic elds applied along the z axis, the transverse staggered eld being along the x axis. They showed that, for example, at 3.5 T one sharp coherent mode B2 with M2 =1.5M appears in Sxx spectrum besides the B1 B1 breather-breather continuum above 1.68M and the soliton-antisoliton continuum above 2M , and two sharp coherent modes B1 and B3 with M1 =0.85M and M3 =1.9M , respectively, appear in Syy spectrum besides the soliton-antisoliton continuum above 2M and the B1 B2 continuum above M1 +M2 . The results agree with the argument by OA that the odd- and even-breathers contribute respectively to the single particle excitation in Syy and Sxx . The masses of these coherent modes should be favorably compared with the zero-eld values, M1 =M , M2 = 3M and M3 =2M , from eq.(3). Since the ESR response corresponds to 1/2(Sxx +Syy ) in the Faraday conguration, we expect to observe the second and third breathers, B2 and B3 as well as the rst breather B1 . For the longitudinal uctuation Szz , we can not say much, simply because the same method can not be applied. However, as mentioned before, numerical calculations for nite chain by Shiba et al.,88) using the exact-diagonalization method, clearly demonstrate that both longitudinal and transverse uctuations show the existence of isolated lowest branch below a continuum. Hence, we expect the similar characteristics for the longitudinal spectrum, though we only must remember that soft mode for the Szz (q, ) progressively moves from the zone boundary (q=) to the zone center (q=0), while for the transverse Sxx (q, ), Syy (q, ), from q=0 to q=

J. Phys. Soc. Jpn. Vol. 72 (2003) Supplement B

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23

also. As a result of such examination, we can now assign all the observed signals to the expected coherent modes: that is, BT , BT , and BT signals in the Faraday cong1 2 3 uration come from the breather modes B1 , B2 , and B3 , respectively. On the other hand, BL and BL in the Voigt 1 2 conguration come from the solitom/antisoliton modes with the same mass as B1 and B2 . In accordance with this assignment, the experimentally determined masses T of BT , BL , BT , BL , and B modes are not so far from 1 1 2 2 3 T L T L M1 =M1 =M1 , M2 =M2 = 3M1 and M3 =2M1 , respectively. As for the signal E, we found that its resonance frequency systematically changes as a function of the magnetic eld and always corresponds to the dierence between the excitation energies of B1 and B2 . Hence, the signal E is identied with ESR transition between the excited states B1 and B2 , being consistent with the unusual temperature dependence of the signal intensity. All these results show, for the rst time, that the predicted low-energy quantum SG excitations, soliton/antisoliton and breather accompanied by higher order, are now experimentally proved to exist in the real system Cu-benzoate in the wide eld and temperature ranges. 3.3.4 Applicability of the quantum SG model Shiba et al.88) discussed the physical origin of the eld-energy gap in a quite dierent way from the SG model. Their interpretation is summarized as follows. The uniform eld together with staggered perpendicular eld determines uniquely the direction of each spin, producing an ordered AFM moment and massive excitations whose energies are scaled with the applied eld. Therefore, they claim that there is no reason to think that the standard linear-mode analysis equivalent to the AFMR for q=0 does not work, although the system is 1D so that corrections due to quantum uctuations should be present. The AFMR theory for q=0 easily predicts two 2 modes given by 1 = 2Jh and 2 = H 2 + 1 where h represents the staggered eld. 1 corresponds to the energy gap at q=0 (q=) for longituginal (transverse) uctuations and, conversely, 2 corresponds to the enrgy gap at q= (q=0) for longitudinal (transverse) uctuations. The 1 mode can be excited in the Voigt conguration, while the 2 mode can be observed in the Faraday conguration. Indeed, both the resonance formula and the polarization dependence agree with the present experiment, apart from the H-dependence. Due to the important eects of quantum uctuations in 1D system which are not taken into account in the linear mode analysis, the eld dependence of the gap is not correctly reproduced: that is, the gap is expected to change as H 1/2 in the linear mode analysis, while it change as H 2/3 in both the SG model and experiment. However they expect the exponent should change from 2/3 to a smaller value as the magnetic eld increases because the linear-mode analysis is expected to be more reliable for a large h. This expectation features qualitatively the deviation at high eld. In fact, we know a classic example of 2D S=1/2

Heisenberg AFM, Cu(HCOO)2 4H2 O9395) in which the eect of the eld-dependent staggered eld was rstly studied in 1971. This substance has quite a similar situation to Cu-benzoate in the point of view that it has the DM interaction as well as the alternating g-tensor, associated with the low symmetry of the crystal structure and the presence of two crystallographically inequivalent Cu sites on the square lattice. Owing to its own denition, the staggered eld couples directly to the sublattice moment known as the Nel order parameter and, therefore, e is expected to produce an ordered AFM moment even in the paramagnetic state. The 3D ordering at TN due to inevitable weak interactions increases as the eld increases but the phase transition is progressively smoothed out. In the strict sense, phase transition disappears as in the case of ferromagnetic transition in a magnetic eld, since symmetry breaking no longer occurs. All these statements were veried in Cu(HCOO)2 4H2 O, using NMR and neutron diraction. However, important dierence in Cu-benzoate is that neutron scattering and SR experiments have failed to detect a Nel transition down e to 20 mK. Although the standard spin-wave analysis misses certain features caused by quantum uctuations in 1D system, it is still instructive to visualize the physical situation in real spin system. In fact, breather is the bound state of soliton and antisoliton as the elementary particles. This fact reminds us of the relation between magnons and solitons. As mentioned already, the magnon is the conned state of solitons. In this context, therefore, the breather which is the conned state of soliton/antisoliton corresponds to the spin-wave magnon. However, we notice a fundamental dierence between breathers and spin-wave magnons. An internal degree of freedom in the breather produces quantized breathers as mentioned above, while that in the magnon does the triplet continuum. In addition, importance of quantum uctuations should be disregarded. As mentioned before, Anderson spin wave is applicable to the 1D classical chain, though the theory assumes simply the ordered Nel state. Howe ever, the limitations of the linear spin wave theory are intrinsically evident in 1D, where the quantum uctuations are strongest. Nevertheless, quite surprisingly, dCP spin wave has the same dispersion as the Anderson spin wave apart from the fact that amplitude increases by a factor /2. This resemblance, however, is only supercial as is well known. It implies that the semi-quantitative accordance does not necessarily mean the same physics or even qualitative accordance. Also, importance of quantum uctuations is exemplied for the Ising model in the transverse magnetic eld. Classical ground state is simply modied to cant the spins toward the x axis. Quantum mechanically, however, x component plays an essential role to induce uctuations due to an exchange of the spin direction. Under such circumstances, our data were interpreted, at the present stage, on the basis of the SG model, though the model is applicable to the low eld. In this view, it is surprising that the mass formula for the quantum SG model valid in the rather wide eld range.

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3.3.5 Related ESR experiments ESR study of the eect of staggered eld in the S=1/2 AF chain is now promoted to the closely related substance, Cu-pyrimidine96) and also to the quite dierent system, BaCu2 (Si1x Gex )2 O7 .97) In these substances, it is shown that the peculiar behaviors of temperaturedependent line width and resonance shift can be well interpreted by OA theory as in the present case. 4. Summary

Our recent work was reviewed with focus on unique features of the application of ESR technique for quantum spin systems. Following a brief survey of historical backgrounds and of recent progress in ESR and model systems, the rst direct observation of quantum sineGordon excitations was demonstrated in a classic example of quantum model substance, Cu-benzoate by application of high-frequency and high-eld ESR technique. In the history, it was very impressive for the present author to notice the fact that the experimental ndings in 1970s, ESR anomaly of Cu-benzoate and the staggered-eld eect in Cu(HCOO)2 4H2 O, are now revitalized after three decades later as a sine-Gordon model. I have recognized very clearly that the pioneer work of the rst generation, Haseda-Date-Hirakawa and others was steadily developed by the second generation, Mekata-Nagata-Motokawa-Katsumata-Endoh-late Ikeda and others and now continuously followed by the third generation, especially Ohta-Nojiri-Kindo in the research eld of high-eld ESR in Japan. Acknowledgements It is my pleasure to be a contributor in the special issue on the occasion of celebrated retirement of Prof. Motokawa and also a pleasure to acknowledge the contributions of many collaborators, especially the authors in Ref. 89. This work was partly supported by a Grant-inAid for Scientic Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan, by The Sumitomo Foundation, and by the REIMEI Research Resources of Japan Atomic Energy Research Institute. Dedicated to Professor M. Motokawa on the occasion of his retirement. This review has been partially presented at the International Workshop on Application of Submillimeter Wave Electron Spin Resonance for Novel Magnetic Systems, Sendai, Japan, June 13-14, 2002, as an Invited Talk. In the historical description, I did not intend to enter into details of history, nor to give a complete list of investigations. Instead I intended to refer to Japanese work, simply for memorial purpose on the occasion of celebrated retirement of Prof. Motokawa. I apologize to many scientists, especially to whom in foreign countries, for not mentioning their work.

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