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# Cooperative Jahn-Teller transition and resonant x-ray scattering in thin film LaMnO₃

## Abstract

Epitaxial thin films of stoichiometric $`\mathrm{LaMnO}_3`$ were grown on $`\mathrm{SrTiO}_3(110)`$ substrates using the pulsed laser deposition technique. From the high resolution x-ray diffraction measurements, the lattice parameters were determined as a function of temperature and the cooperative Jahn-Teller transition was found to occur at $`T_{JT}`$=573.0 K. Also measured was resonant x-ray scattering intensity of the orthorhombic (100) peak of $`\mathrm{LaMnO}_3`$ near the Mn K edge from low temperatures to above $`T_{JT}`$. We demonstrate that the integrated intensity of the (100) peak is proportional to the 3/2 power of the orthorhombic strain at all temperatures, and thus provide an experimental evidence that the resonant scattering near the Mn K edge in $`\mathrm{LaMnO}_3`$ is largely due to the Jahn-Teller effect.

Orbital degrees of freedom representing anisotropically shaped $`3d`$ orbitals are of importance for understanding magnetic, structural, and electronic properties of transition metal oxides tokura . For instance, superexchange interactions between electrons occupying neighboring transition metals are very sensitive to the orientation of occupied $`3d`$ orbitals goodenough1 ; kanamori ; khomskii , and the magnetic properties are strongly coupled to the orbital degrees of freedom. Also important regarding orbital degeneracy is the well-known Jahn-Teller (JT) distortion jahn ; moreover, these local distortions may even behave cooperatively leading to a structural transition. Electronic transport properties of transition metal oxides, of course, is also strongly affected by the relative orientation of occupied orbitals on neighboring ions; the double exchange mechanism is a good example zener .

Despite a recognized role that the orbital degrees of freedom play in transition metal oxides, securing a direct experimental probe for orbital order has long been problematic; however, Murakami et al. proposed in a recent series of experimental works that resonant x-ray scattering (RXS) is a direct probe of orbital order murakami . The RXS signal near the Mn K edge in perovskite manganite samples was interpreted to be sensitive to the status of $`3d`$ electrons and their orbital ordering. Since the transition was supposed to be a dipolar one from $`1s`$ to $`4p`$, the origin of the sensitivity of RXS to $`3d`$ orbital order became controversial. Murakami et al. originally interpreted the RXS data based on the localized $`4p`$ states and their subsequent splitting due to the interaction with $`3d`$ orbitals. Ishihara et al. then specified the interaction to be the Coulomb repulsion between $`3d`$ and $`4p`$ states ishihara . However, this $`3d`$ orbital ordering interpretation was immediately questioned by Elfimov et al. sawatzky ; they used band calculations to show that the JT effect (JTE) is a major player in RXS. (JTE is used here to include both local JT distortion of $`\mathrm{MnO}_6`$ octahedra and their subsequent cooperative ordering.) Indeed it is expected that $`4p`$ states form a broad band in solids, and the $`3d4p`$ direct Coulomb interactions in the band would not be as strong as in localized states; a number of band calculations for $`\mathrm{LaMnO}_3`$ now assert that Mn $`4p`$ states strongly hybridize with the neighboring O orbitals and the RXS intensity and its polarization dependence are determined mostly by this Mn$``$O hybridization and thus by JTE, rather than by the orbital order of the $`3d`$ states sawatzky ; benfatto ; takahashi ; benedetti .

$`\mathrm{LaMnO}_3`$, a parent material of colossal magnetoresistance manganese oxides, has been at the center of orbital physics from the beginning, that is, Goodenough invoked orbital order to account for the A-type antiferromagnetic order in $`\mathrm{LaMnO}_3`$ goodenough2 . Thus $`\mathrm{LaMnO}_3`$ appears to be a good system for the observation of orbital ordering, and Murakami et al. measured RXS from a single crystalline $`\mathrm{LaMnO}_3`$ to investigate orbital ordering. However, this system undergoes a concomitant cooperative JT transition powder , and the characteristics of RXS can also be explained in terms of the JTE as noted above. In the present study we attempted to address this point experimentally by focusing specifically on the relationship between the lattice distortion from the JTE and the RXS intensity. We demonstrate that the RXS signal is in proportion to the 3/2 power of the lattice orthorhombicity in $`\mathrm{LaMnO}_3`$ at all temperatures; this result provides an evidence that the long range order of JT distorted MnO6 octahedra and the associated band effect are indeed a dominant factor in RXS.

The samples used in the present experiment were epitaxial thin films of $`\mathrm{LaMnO}_3`$ deposited on $`\mathrm{SrTiO}_3`$ substrates. Using a $`\mathrm{LaMnO}_3`$ bulk pellet as a target, thin films of thickness approximately 2000 Å were deposited on $`\mathrm{SrTiO}_3(110)`$ single crystal substrates by the pulsed laser deposition method koo . The substrates, of typical dimension 5 mm x 5 mm, were annealed for approximately 10 hours at $`1000^\mathrm{o}\mathrm{C}`$ in oxygen environment to obtain atomically flat surfaces, and then films were deposited on the substrates at $`800^\mathrm{o}\mathrm{C}`$ and 180 mTorr of oxygen pressure. Since as-grown $`\mathrm{LaMnO}_3`$ films may contain excessive oxygen, post-deposition thermal treatment was done at about $`950^\mathrm{o}\mathrm{C}`$ in flowing argon. The post-annealing procedure also improved the structural quality of the films; the mosaic width (FWHM) of the (200) reflection was about $`0.2^\mathrm{o}`$. X-ray scattering measurements were performed on the beamline 3C2 at the Pohang Light Source. The incident beam is focused by a bent mirror and is monochromatized by a Si(111) double crystal. The energy was calibrated using a manganese foil and the resolution was about 2 eV.

At this point, remarks on the choice of the substrate and film orientation are in order. It is known from the neutron study of bulk samples that $`\mathrm{LaMnO}_3`$ below the structural transition temperature (ca. 750 K) has an orthorhombic $`Pbnm`$ crystal structure, and the orthorhombic unit cell volume is $`\sqrt{2}`$ x $`\sqrt{2}`$ x 2 times as large as that of the perovskite cubic cell powder . We designate these directions and lattice parameters as $`a`$, $`b`$, and $`c`$, and the parameters satisfy the relation, $`a>b>c/\sqrt{2}`$. (The Miller indices used for $`\mathrm{LaMnO}_3`$ in this paper are orthorhombic ones.) Neutron powder diffraction also indicated that the JT distortion of MnO6 octahedra accompanies the structural change from a high $`T`$ pseudocubic phase to a low $`T`$ orthorhombic one, and thus the transition is a cooperative JT type. In the orthorhombic phase, antiferro-type $`3d`$ orbital ordering and concomitant ordering of the distorted octahedra occur in the $`ab`$-plane goodenough2 . Thus in order to investigate these ordered states in the $`ab`$-plane, one must probe the normally forbidden $`(h00)`$ or $`(0k0)`$ peaks with odd $`h`$ and $`k`$. From this consideration, it is preferred to have $`a`$\- or $`b`$-direction as a surface normal; one should deposit $`\mathrm{LaMnO}_3`$ on the (110) surface of a cubic substrate, rather than on the usual (100) surface. Then the surface-normal cubic  direction of the substrate would corresponds to the orthorhombic  direction of the film. $`\mathrm{SrTiO}_3`$ was chosen as substrate, because its lattice constant (3.905 Å) closely matches the lattice spacing of $`\mathrm{LaMnO}_3`$.

Fig. 1 is the contour plot of x-ray diffraction data obtained at 6.529 keV of photon energy. It shows the reciprocal space mapping in the vicinity of the substrate (200) reflection at two temperatures. It is seen from Fig. 1(a) that the (220) peak of the $`\mathrm{LaMnO}_3`$ film (in orthorhombic notation) is in registry with the cubic (200) peak of $`\mathrm{SrTiO}_3`$ at $`T`$ = 573.2 K. The lattice spacings of the $`\mathrm{LaMnO}_3`$ film at this temperature is nearly equal (3.928Å, 3.917Å, and 3.912Å), and the system is pseudocubic. At room temperature, on the other hand, we find two diffraction peaks, instead of one, from the film as plotted in Fig. 1(b). This indicates that one has two domains of different orientations, denoted as $`A`$ and $`B`$ domains (corresponding to $`F_a`$ and $`F_b`$ in the figure, respectively). Clearly this is the result of the effort of the system which tried to reduce the strain energy as much as possible when the system underwent the transition from a pseudocubic to orthorhombic phase. Domain formation is often found in a thin film which undergoes a structural change domain . The difference between the two domains lies in their relative orientation, and we focus on the $`A`$ domain only. The lattice constants and orientation of the $`A`$ domain were determined from in-plane and out-of-plane reflections. The lattice constants in terms of the cubic cell parameters were 3.983Å, 3.912Å, and 3.866Å; the domain had its $`c`$-axis (with the shortest lattice spacing) parallel to  in the substrate surface, and the $`a`$-axis parallel to the substrate surface normal . Thus the $`ab`$-planes of the $`A`$ domain stood perpendicular to the substrate surface.

In order to characterize the phase transition, we carried out x-ray diffraction measurements as a function of temperature. In Fig. 2 plotted are $`a`$ and $`b`$ lattice constants and the orthorhombic strain $`(ab)`$ against temperature, and it is seen that the structural transition occurs at $`T_{JT}`$ = 573.0 K. This transition, of course, corresponds to the cooperative JT one which occurred at 750 K in bulk ceramic samples. This reduction in transition temperature is not at all surprising, considering the fact that a thin film is generally under biaxial stress due to lattice mismatch with the substrate and/or differential thermal expansion between the film and substrate. The fact that a single crystal bulk sample shows the transition at 780 K murakami , 30 K higher than the ceramic case, clearly illustrates the role of stress in determining the transition temperature. If the lattice constants of the epitaxial film at room temperature (given above) are compared with those of a bulk sample at the same temperature (4.060Å, 3.912Å, and 3.834Å) elemans , it is recognized that the orthorhombicity of the film is much less than that of the bulk. Thus the underlying $`\mathrm{SrTiO}_3`$ substrate has the effect on the film of suppressing the JT transition. The decrease of the transition temperature in thin film case is also in accord with a recent pressure study of $`\mathrm{LaMnO}_3`$ that the coherent JT distortion is reduced with increasing pressure loa .

Having characterized the cooperative JT transition, we turn to the discussion of RXS near the Mn K edge; here we focus on the structurally forbidden (100) peak of $`\mathrm{LaMnO}_3`$. Note that the momentum transfer direction for this peak of the $`A`$ domain is the surface normal. Fig. 3 displays the characteristics of absorption and RXS obtained at 15.5 K from the (100) peak of the $`A`$ domain. Fig. 3(a) is the plot of fluorescence data of Mn3+ K absorption as a function of incident photon energy. The shape of the curve including the splitting into two peaks matches the $`4p`$ total density of states from the band calculation, indicating the dipolar nature of the process ($`1s4p`$) sawatzky . The (100) peak exhibits a resonance-type enhancement in the integrated intensity as a function of energy and reaches a maximum at 6.555 keV as illustrated in Fig. 3(b). Since the incident synchrotron beam is $`\sigma `$-polarized (polarization perpendicular to the scattering plane) and RXS occurs via the $`\sigma \pi `$ channel, the RXS intensity should exhibit an oscillation in intensity as the $`ab`$-plane is rotated around the momentum transfer direction, i.e., the surface normal. Fig. 3(c) shows the results of the azimuthal scan measured at 6.555 keV of energy, revealing a sinusoidal variation with a two-fold symmetry. The integrated intensity plotted in the figure was normalized with the (200) fundamental charge reflection in order to correct for small variations due to the film shape. The azimuthal angle $`\psi =0^o`$ was defined to be when the $`ab`$-plane is perpendicular to the scattering plane.

The features displayed in Fig. 3, resonance enhancement of the (100) peak and the two-fold symmetric nature of the integrated intensity as a function of azimuthal angle, follow from the fact that RXS is a second order process driven by the $`\stackrel{}{A}\stackrel{}{p}`$ term in the Hamiltonian; however, the same result can be derived either from the antiferro-type $`3d`$ orbital ordering or from the coherent ordering of the JT distorted $`\mathrm{MnO}_6`$ octahedra in the $`ab`$-plane. The essential ingredient in the theory is a breaking of the equivalence of two Mn sites (and the associated non-spherical $`4p`$ states) in the orthorhombic $`ab`$-plane, and this can be done by either of the two ways. Since these two types of order coexist in $`\mathrm{LaMnO}_3`$, it appears to be difficult to distinguish them as a origin of RXS. On the other hand, if one remembers that coherent ordering of local JT distortions brings about the structural transition, while orbital ordering itself seems to occur even without lattice distortion endoh , then one is led to a conclusion: if the JTE is indeed the cause of RXS in $`\mathrm{LaMnO}_3`$, there must exist a certain relationship between the intensity of RXS and the degree of lattice distortion which would be proportional to the degree of local JT distortion. Thus, we focused our attention on revealing this relationship from the experimental data; the results are illustrated in Fig. 4.

Fig. 4(a) is the plot of the integrated intensity of the (100) peak as a function of temperature. The integrated intensity was measured at 6.555 keV of photon energy and the azimuthal angle was set at $`\psi =0^o`$. The intensity disappears exactly at the same temperature $`T_{JT}`$ where the orthorhombic strain does, as temperature is increased. Fig. 4(b) is the simultaneous plot of the integrated intensity and the normalized orthorhombic strain $`e(ab)/(a+b)`$ as a function of temperature. Note that the vertical axis for the normalized strain is not $`e`$, but $`e^{3/2}`$. The fact that these two data sets can be superposed at all temperatures means that the RXS intensity is proportional to $`e^{3/2}`$; the inset, the plot of $`e^{3/2}`$ against the intensity, further highlights the proportional relationship. This simple relationship we exposed here, particularly the nontrivial exponent 3/2, must be able to distinguish the two proposed origins of RXS. In fact, the ab initio band calculation on $`\mathrm{LaMnO}_3`$ by Benedetti et al. benedetti , which identified the JTE as the origin of RXS near the Mn K edge, predicted the proportional relationship between the integrated instensity and $`e^{1.5}`$. The present work then should be regarded as a definite experimental evidence that the resonant scattering near the Mn K edge in $`\mathrm{LaMnO}_3`$ is due to the Jahn-Teller effect, rather than $`3d`$ orbital ordering.

One final remark on the relationship between the lattice orthorhombicity and the local JT distortion should be made, because one of these two aspects of $`\mathrm{LaMnO}_3`$ does not automatically suggest the other. The orthorhombic symmetry may be induced from cubic perovskites just by a tilting of regular, not distorted, oxygen octahedra, e.g., $`\mathrm{CaTiO}_3`$ cto . In fact, even the high $`T`$ phase of $`\mathrm{LaMnO}_3`$, where oxygen octahedra are regular, belongs to the $`Pbnm`$ class, not a cubic one powder . These systems, however, are in sharp contrast to $`\mathrm{LaMnO}_3`$ below $`T_{JT}`$, that is, their three lattice parameters are very close in size to each other despite orthorhombicity, and they may be called pseudocubic. The significant lattice orthorhombicity in low $`T`$ $`\mathrm{LaMnO}_3`$ is the direct result of the local JT distortion: the long and short Mn-O bonds alternate in the $`ab`$-plane and contribute to $`a`$ and $`b`$ lattice parameters in different proportions due to the tilting of octahedra argyriou . It is also noted that both the difference $`(ab)`$ of the lattice parameters and the difference in Mn-O bond lengths disappear simultaneously and continuously as $`T`$ is increased toward $`T_{JT}`$. Evidently the lattice orthorhombicity and the degree of local JT distortion are proportional to each other.

In conclusion, we have demonstrated that the RXS intensity is proportional to the 3/2 power of the orthorhombic strain, and thereby showed that RXS near the Mn K edge is due to the JTE, rather than $`3d`$ orbital ordering.

We acknowledge the financial support from KOSEF via eSSC, the special fund of POSTECH, and the BK21. Experiments at the PLS were supported by MOST and POSCO. We thank Y.J. Park for technical assistance.

Figure Captions

FIG. 1: The contour plot of x-ray diffraction data around the cubic (200) reflection of $`\mathrm{SrTiO}_3(110)`$. $`q_{}`$ and $`q_{}`$ are parallel to the  and \[1$`\overline{1}`$0\] directions, respectively. (a) At 573.2 K, a single peak in registry with the substrate (200) peak is found from the film. Inset illustrates the momentum transfer of the substrate (200) peak. $`F`$ and $`S`$ denote the peaks from the film and substrate, respectively. (b) At room temperature, the two peaks (denoted as $`F_a`$ and $`F_b`$) from two domains with different orientation are seen. Inset shows diffraction data along the surface-normal direction.

FIG. 2: The lattice constants $`a`$ and $`b`$ and the orthorhombic strain $`(ab)`$ as a function of temperature. The cooperative Jahn-Teller transition occurs at $`T_{JT}`$ = 573.0 K. This transition temperature is somewhat low compared to 750 K of a bulk sample. This is due to the fact that the film is under biaxial stress. The lines are guide to the eye.

FIG. 3: X-ray absorption and resonant scattering near the Mn K edge. The data were obtained from the structurally forbidden (100) peak of the $`A`$ domain at 15.5 K. (a) The fluorescence data is plotted as a function of photon energy. The shape of the curve matches well the $`4p`$ total density of states from the band calculation, indicating the $`1s4p`$ process. (b) The integrated intensity for the (100) peak as a function of energy. The intensity exhibits a resonance-type enhancement around a maximum at 6.555 keV. (c) The integrated intensity of the (100) peak measured as a function of azimuthal angle is shown. The solid line represents a fit of the data to $`\mathrm{cos}^2\psi `$.

FIG. 4: (a) Temperature dependence of the integrated intensity for the (100) peak. The intensity disappears at $`T_{JT}`$ where the orthorhombic strain does, as temperature is increased. (b) The integrated intensity and the 3/2 power of the normalized orthorhombic strain $`e=(ab)/(a+b)`$ are plotted as a function of temperature simultaneously. The complete coincidence of these two data sets at all temperatures is further highlighted in the inset by plotting $`e^{3/2}`$ vs. intensity.


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# Bootstrap equations for effective theories and the calculation of the 𝐺_𝑇/𝐺_𝑉 ratio

## 1 Preliminary notes

It is widely believed that to construct the complete theory of strong processes one needs to make two steps:

1. With the help of QCD (which is supposed to be the fundamental theory of strong forces) find the hadronic spectrum (poles of the Green functions) and construct the complete set of asymptotic states.
2. Construct the scattering theory for those (composite) states.

It is not yet clear how to solve the first problem. Is it possible to say anything about the scattering theory of hadrons, having no information on their inner structure? That is how the effective theory111 Here this term is understood precisely in the same sense as in . concept naturally comes to mind.

When constructing a theory of hadron scattering, we are forced to rely upon the Dyson series for the $`S`$-matrix, because this is the only known perturbative approach guaranteeing unitarity, causality and Lorentz-invariance of the results (see, e.g., ). In the case of effective theory this series can always be presented in the form

$$S_{fi}=f|T_\stackrel{}{W}\mathrm{exp}\left\{iH_{\mathrm{int}}𝑑x\right\}|i,$$
(1)
where $`T_\stackrel{}{W}`$ stands for Wick’s (explicitly covariant) T-product and the Hamiltonian density (in the interaction picture) $`H_{\mathrm{int}}`$ does not contain any noncovariant terms. Imposing any algebraic222Linearly realized, for example isotopic $`SU_2`$ (or $`SU_3`$). symmetry requirements on a theory based on the form (1) looks not more difficult than if the Lagrangian picture is used: the $`S`$-matrix is covariant and satisfies the symmetry requirements, if $`H_{\mathrm{int}}`$ does.

In contrast, the problem of dynamical symmetries looks much more transparent in the Lagrangian picture. And the transition from the Lagrangian picture to the Hamiltonian one looks almost hopeless when one deals with an effective theory. Indeed, in this case one needs to solve an infinite system of constraints arising, in particular, due to the presence of higher powers of time derivatives. However, as shown in , one needs only a finite number of Lagrangian terms when working to a given order in a small momentum. Thus, in the last case one can construct the corresponding Hamiltonian and, hence, avoid problems with unitarity. This program (first realized in ) gives us the natural way (“matching”) to take into account the dynamical symmetry requirements in the effective theory based on the Hamiltonian. Namely, one needs to compute the amplitude of the process in question, expand it in powers of a small momentum (of the Goldstone particle) up to a given order, and, finally, compare the result with that following from the canonical approach (based on the invariant Lagrangian of the same order) and equate the corresponding constants.

Which fields should be included in the Hamiltonian? To be able to work not only in the low energy region, we include the resonance fields (like the $`\rho `$-meson) as well as the fields of the true asymptotic states (stable with respect to the strong forces, like the $`\pi `$-meson).333 No problem with unitarity occurs in spite of the fact that Dyson’s series is based on the Hamiltonian depending on resonance fields (see, e.g. ). In fact, this approach is used in the Standard Model of electroweak interactions: for instance, the $`W`$-boson is not an asymptotic state. To avoid model dependence of the results, we reserve the possibility to work with an arbitrary (possibly infinite) number of resonances with arbitrarily high values of spin $`J`$ and mass $`M`$. The only limitation is suggested by experiment: we imply that there is a finite number of resonances with the same mass (though the mass spectrum may be unbounded). To put it another way, we imply the existence of a leading Regge trajectory (in the real plane of $`\mathrm{Re}M`$ and $`J`$) which, however, is not necessarily linear. According to the phenomenology of strong interactions we do not deal with massless spin $`J>\frac{1}{2}`$ particles. Also, we assume that the maximal isospin value is $`I=1`$ for mesons and $`I=\frac{3}{2}`$ for baryons.

Thus, we consider the effective hadron scattering theory based on Dyson’s series (1) with the Hamiltonian written in the form of an infinite sum of Lorentz-invariant (and SU(2)-invariant) local terms, each one constructed from the fields (and all powers of their derivatives of arbitrary high order) of pions, $`K`$-mesons, nucleons and all possible resonances.

## 2 Essential parametres, self-consistency and the bootstrap equations

It is possible to show that the essential parametres444These are the only parametres that appear in the $`S`$-matrix elements, see , Chapter 7. of the effective scattering theory are masses (real parts of pole positions) and those (and only those) combinations of coupling constants which are needed to fix the on-shell kinematic structure of tree-level vertices. When computing the $`S`$-matrix elements one does not need to impose a renormalization condition on each coupling constant appearing in the Hamiltonian: only the essential parametres require fixing of their finite parts.

The central idea of our work is that one cannot take independent renormalization prescriptions even for the essential parametres of the effective scattering theory: certain natural self-consistency requirements impose an infinite number of constraints (bootstrap conditions) on the allowed physical values of the essential parametres. Namely, to make it possible to construct the one-loop approximation for the amplitude of a given scattering process (here we only discuss $`22`$ processes), the corresponding tree-amplitude $`A(s,t,u)`$ must satisfy the following two requirements555Both of them are trivial if there is a finite number of terms in the Hamiltonian (Lagrangian).:

1. It must be a meromorphic function666No singularities except poles. of the Mandelstam variables $`s,t,u`$, with poles and residues fixed by the Feynman rules.
2. This amplitude must be polynomially bounded777Polynomial boundedness of the meromorphic functions is understood as in complex analysis, see e.g. . in each independent energy-like variable at zero value of the corresponding momentum transfer.

As explained in , these two requirements turn out to be sufficient to derive the exact form of the tree-amplitude. At the same time they lead to an infinite set of equations connecting the tree-amplitude parametres among themselves (bootstrap equations). And if we write the Hamiltonian in terms of physical parametres (plus the necessary counterterms — what we can always do), then the tree-amplitude is automatically written in terms of physical (experimentally measurable) parametres. All this means that the bootstrap equations are not affected by the renormalization procedure and can be tested experimentally.

## 3 Comparison with experiment

In the cases of $`\pi \pi `$ and $`\pi K`$ elastic scattering (see ) it has been found that the resulting equations strongly contradict the known data unless two light scalar resonances are taken into account. These are the $`\sigma `$ ($`0^+0^+`$) and $`\kappa `$ ($`0^+\frac{1}{2}^+`$) mesons with the following parametres estimated from the bootstrap equations: $`m_\sigma `$ 500 MeV; $`\mathrm{\Gamma }_\sigma `$ 300 MeV; $`m_\kappa `$ 1 GeV; $`\mathrm{\Gamma }_\kappa `$ 500 MeV.

These parametres are strongly supported by modern data, see, e.g. . It is interesting to note, that, as was shown in  (see also ), to preserve the unitarity bound for the $`\pi \pi `$ and $`\pi K`$ amplitudes one must take into account both the resonance and the (automatically implied in our approach) background interaction terms.

Perhaps, the most interesting result has been obtained from the analysis of the bootstrap equations for the $`\pi N`$ scattering amplitude parametres. It was possible to make the accurate estimate of the ratio $`G_{NN\rho }^T/G_{NN\rho }^V=6(\pm 20\%)`$, of tensor/vector $`NN\rho `$ coupling constants888For the corresponding experimental data and notations see .. This value turned out to be in nice agreement with experimental data. As far as we know, such a relation has never been explained in terms of model-independent theoretical arguments.

Besides, with the help of the bootstrap equations we have estimated the values of 40 coefficients in the expansion of the $`\pi N`$ amplitude around the crossing symmetry point, first introduced in . The detailed analysis will be published elsewhere.

### Acknowledgments

I wish to thank V. Cheianov, P. Osland, F. Sannino, J. Schechter, V. V. Sukhanov, A. N. Vassilev and especially V. Vereshagin for stimulating discussions. This work was supported in part by RFBR (grant 01-02-17152), INTAS (INTAS call 2000, project 587), and by Russian Ministry of Education (programme “Universities of Russia” and grant E00-3.3-208).


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# An Efficient Strategy to Select Targets for Gas-Dynamical Measurements of Black Hole Masses Using the Hubble Space Telescope1footnote 11footnote 1Based on observations made with the Hubble Space Telescope, which is operated by AURA, Inc., under NASA contract NAS5-26555.

## 1 Introduction

The installation of the Space Telescope Imaging Spectrograph (STIS; Leitherer et al. 2001) on the Hubble Space Telescope (HST) ushered in a new era in the search for massive black holes (BHs) in galactic nuclei. By now, sufficiently large numbers of BH candidates are known that the emphasis has shifted from detections of individual objects to demographic studies using statistical samples (e.g., Richstone et al. 1998; Ho 1999; Gebhardt et al. 2000b; Ferrarese & Merritt 2000). Future progress will focus on two fronts, first on sharpening the analysis techniques to improve the accuracy of the mass measurements, and second on substantially enlarging the existing samples to cover galaxies across the Hubble sequence.

BH searches with HST use either stars or gas to trace the central potential. These two approaches are complementary, each with its merits and limitations. Modern, fully general, stellar-dynamical models are powerful because they give information not only on masses but also on the orbital structure of the galaxy (e.g., van der Marel et al. 1998; Cretton & van den Bosch 1999; Gebhardt et al. 2000a). One drawback is that both the data and the computational requirements are expensive. Another is that the modeling can be very challenging for complicated dynamical structures; the double nucleus of M31 serves as a good illustration (e.g., Kormendy & Bender 1999; Bacon et al. 2001). This technique also cannot easily cope with dusty galaxies, as a consequence of which most stellar-dynamical work with HST has been biased toward early-type (mostly elliptical) galaxies.

Gas kinematics in principle offer a more straightforward measure of the central mass, provided that the gas participates in Keplerian rotation in a disklike configuration. The observations are less demanding because optical emission lines from ionized gas generally have much higher equivalent widths than stellar absorption lines. Moreover, as demonstrated later in this paper, optical nebular emission invariably traces nuclear dust features. This technique, therefore, can be applied to galaxies inaccessible to stellar observations. Unlike stars, however, gas behaves as a collisional fluid and responds to nongravitational perturbations such as shocks, radiation pressure, or magnetic fields. Despite these potential complications, gas-dynamical models have been applied to a number of elliptical galaxies with circumnuclear gas disks (Harms et al. 1994; Ferrarese, Ford, & Jaffe 1996; Macchetto et al. 1997; van der Marel & van den Bosch 1998; Bower et al. 1998; Ferrarese & Ford 1999; Verdoes Kleijn et al. 2000).

Our group has concentrated on using STIS to apply the gas-dynamical technique to the bulges of spiral and S0 galaxies (Shields et al. 2000; Barth et al. 2001; Sarzi et al. 2001, 2002). Our work has revealed a subtlety that has not been widely appreciated in previous studies: the majority ($``$80%) of randomly chosen disk galaxies do not have well-behaved velocity fields suitable for gas-dynamical modeling at HST resolution. Based on this experience, we have developed an efficient strategy to preselect galaxies that significantly increases the chance of success for future STIS programs. This paper describes our technique, which is based on the use of the dust morphology to predict the velocity field.

## 2 The Data

The data used in this paper derive from our Cycle 7 STIS program GO-7361. Since a full description of the observations and data reductions will be given elsewhere (Rix et al. 2002; see also Sarzi et al. 2001, 2002), here we only mention a few key points pertinent to the present discussion. Our sample was designed to address a diverse set of scientific goals, among them measurement of BH masses in bulges. It comprises nearly all northern, bright S0–Sb galaxies within 17 Mpc that are known to have nuclear emission in the spectroscopic catalog of Ho, Filippenko, & Sargent (1997). We avoided galaxies later than Sb because their bulges are expected to be faint or absent, and because their higher dust content may compromise our ability to center the narrow slit on the nucleus. To further ensure that the nucleus will be easily accessible, we eliminated galaxies more inclined than 60. The visibility of the nucleus was also confirmed by inspection of WFPC2 images, which were available for most of the galaxies. The final sample contained 24 galaxies, of which 23 (Table 1) were successfully observed; the acquisition of NGC 4138 failed because a nearby, bright star was mistaken for the nucleus.

Following a brief target-acquisition image using the F28X50LP long-pass filter, the primary kinematics data for each galaxy consist of a single-orbit integration with the G750M grating ($`\lambda `$$`\lambda `$6300–6870 Å; FWHM $`\mathrm{\Delta }\lambda 2.2`$ Å) using the 0$`\stackrel{}{\mathrm{.}}`$2$`\times `$52′′ slit. To enable flexibility in scheduling, we did not choose specific position angles for the slit.

## 3 Dust Morphology and Velocity Field

We detected H$`\alpha `$ and \[N II\] $`\lambda `$$`\lambda `$6548, 6583 emission in all the objects, but the emission was symmetrically extended in the central 0$`\stackrel{}{\mathrm{.}}`$5–1$`\stackrel{}{\mathrm{.}}`$0 in only $``$75% (17/23) of the sample. For these 17 objects, “rotation curves” were derived from the radial velocities of the gas as a function of position along the slit using the H$`\alpha `$ and \[N II\] emission lines. The velocities of these features were derived using SPECFIT (Kriss 1994) within IRAF111IRAF is distributed by the National Optical Astronomy Observatories, which are operated by the Association of Universities for Research in Astronomy, Inc., under cooperative agreement with the National Science Foundation., assuming a common velocity, a Gaussian profile, and a fixed \[N II\] doublet ratio of 3:1. The results are shown in Figure 1. A striking result is the rarity of galaxies with well-behaved velocity fields. Among the 17 galaxies with spatially resolved velocity profiles, only four (NGC 2787, 4203, 4459, 4596), or 25%, show ordered rotation curves amenable to dynamical analysis (Sarzi et al. 2001). The rest of the velocity curves look disorganized and difficult to interpret (Fig. 1). In terms of using the data for BH searches, therefore, the success rate is disappointingly low.

The greyscale panels in Figure 1 display the unsharp-masked optical continuum image of each galaxy. Most of the data are archival broad-band (roughly $`V`$) images acquired with the PC detector on WFPC2; two are our own STIS F28X50LP target-acquisition images. To accentuate high-spatial frequency features such as star clusters and dust lanes, we subtracted from each image a version of itself smoothed by a Gaussian with $`\sigma `$ = 4 pixels ($``$0$`\stackrel{}{\mathrm{.}}`$2). The nucleus, by design, is clearly visible in each image. As was known from previous HST imaging studies of disk galaxies (Phillips et al. 1996; Carollo et al. 1997), dust is ubiquitous. Every galaxy in our sample shows dust lanes at some level within a central radius of $``$5′′, or $``$400 pc for a typical distance of 17 Mpc. However, unlike the case of early-type (E and S0) galaxies (van Dokkum & Franx 1995; Tomita et al. 2000; Tran et al. 2001), the dust distributions do not resemble simple disks with sharply delineated, outer edges. Instead, the dust morphology can be best described as nuclear spirals (e.g., NGC 3351, NGC 3982), concentric rings (e.g., NGC 2787, NGC 4596), or simply chaotic (e.g., NGC 3368, NGC 4450). The one object with a fairly well-defined nuclear disk, NGC 4435, turns out to be an S0 galaxy.

Closer examination of the data reveals that the degree of ”orderliness” of the gas kinematics evidently correlates with the morphology of the dust lanes. All four galaxies with well-behaved velocity fields (NGC 2787, 4203, 4459, 4596) have relatively smooth, circularly symmetric dust rings. The converse seems to hold for most, but not all, objects. For example, the dust patterns in NGC 4245 and NGC 4800 resemble those in the above-mentioned four objects, but neither has a regular, symmetric velocity field in ionized gas. The case of NGC 4435 deserves special remark. Although this galaxy possesses a clean nuclear disk, we were unable to obtain a usable symmetric rotation curve because the slit fell near the minor axis of its highly inclined disk (Fig. 1c). The velocity curve of the far side of the disk indeed looks regular, but that of the near side is obstructed by a prominent dust lane.

Thus, in terms of planning for HST BH searches using gas kinematics, it appears that the morphology of the dust lanes can be used as an efficient and relatively reliable predictor of the gas kinematics. Albeit somewhat subjective, and by no means perfectly foolproof, the strategy we advocate is nonetheless a highly effective tool for culling promising targets for STIS spectroscopy. It is especially attractive in view of the extensive database of optical images of nearby galaxies available in the HST archives and the straightforward manner in which unsharp masking can be performed on them. It would be fruitful to revisit these issues in the future when we have available images and spectra with resolutions higher than that currently possible with HST.

## 4 Summary

Searches for massive BHs in bulges of disk galaxies generally must rely on gas-dynamical methods because these objects are dusty. Our experience with STIS data indicates that the success rate will be low in randomly chosen samples of spiral and S0 galaxies because well-defined nuclear gas disks with regular, symmetric velocity fields are rare in these objects. We show that the degree of regularity in the velocity field correlates with the morphology of the dust lanes, which can be efficiently ascertained through unsharp masking of optical continuum HST images. Objects with smooth, circularly symmetric dust lanes tend to have velocity fields that are amenable to dynamical analysis. By contrast, galaxies with obviously disorganized dust morphology will almost never yield easily interpretable velocity fields. We draw attention to this empirical correlation as a powerful tool to select targets for future HST programs to search for massive BHs using gas kinematics.

This work was supported financially through NASA grant NAG 5-3556, and by grants in support of HST programs GO-7361 and GO-7403, awarded by STScI, which is operated by AURA, Inc., for NASA under contract NAS5-26555. Research by A. J. B. is supported by a postdoctoral fellowship from the Harvard-Smithsonian Center for Astrophysics. A. V. F. is grateful for a Guggenheim Foundation Fellowship.”


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# Realization of a large 𝐽₂ quasi-2D spin-half Heisenberg system: Li2VOSiO4

## Abstract

Exchange couplings are calculated for Li2VOSiO4 using LDA. While the sum of in-plane couplings $`J_1+J_2=9.5\pm 1.5`$K and the inter-plane coupling $`J_{}0.2`$$`0.3`$K agree with recent experimental data, the ratio $`J_2/J_112`$ exceeds the reported value by an order of magnitude. Using geometrical considerations, high temperature expansions and perturbative mean field theory, we show that the LDA derived exchange constants lead to a remarkably accurate description of the properties of these materials including specific heat, susceptibility, Neél temperature and NMR spectra.

71.15.Mb,75.10.Jm,75.30.Et

In many recently discovered magnetic materials the determination of exchange constants, without input from electronic structure calculations, has proven very difficult and has often led to wildly incorrect parameter values. The interplay of geometry and quantum chemistry has yielded many surprises which could not have been anticipated without a full calculation. Examples are the recently discovered vanadates CaV4O9 and CaV3O7. In all these cases the dominant exchange interactions were resolved and a good understanding of the material properties obtained only after analyses of electronic structure calculations were carried out.

Frustrated square-lattice spin-half Heisenberg antiferromagnets with nearest neighbor exchange $`J_1`$ and second neighbor (diagonal) exchange $`J_2`$ have received considerable attention recently. The properties of the model with $`J_2`$=$`0`$ (or $`J_1`$=$`0`$) are well understood at zero and finite temperature . The large $`J_2`$ limit of the model is a classic example of quantum order by disorder, where at the classical level the two sublattices order antiferromagnetically but remain free to rotate with respect to each other. This degeneracy is lifted by quantum fluctuations leading to collinear magnetic order in a columnar pattern. At intermediate $`J_2/J_1`$ there is strong evidence for a spin-gap phase, though the nature of this phase is not fully resolved yet .

While there has been tremendous theoretical interest in these models, there were no known experimental realizations for intermediate to large $`J_2/J_1`$, until the investigation of Li2VOSiO4 by Melzi et al. Studying the splitting patterns of the 7Li NMR spectra, these authors presented strong evidence for columnar order. Combining several experiments they derive exchange couplings (with $`J_2/J_11.1`$) well into the region where model calculations find columnar order.

However, several puzzling pieces in that excellent and detailed study remain: (i) The ratio of exchange constants was not well determined from the susceptibility and specific heat data; we will present electronic structure and many-body calculations to show that their estimate $`J_2/J_11`$, is off by an order of magnitude. (ii) The estimated $`T=0`$ moment was anomalously small for a system well inside the columnar ordered phase. Taking into account the antiferromagnetic inter-plane coupling, we propose that the NMR derived moment is small due to a cancellation of hyperfine fields from neighboring planes. (iii) The order parameter exponent $`\beta `$ at the transition was estimated to be $`\beta 0.25`$, which is intermediate between 2D Ising and typical 3D exponents. We will show that the inter-plane exchange constants differ from the largest ones by less than two orders of magnitude. Thus a strong crossover between 2D and 3D behavior could be expected. (iv) The Neél temperature was nearly field independent up to a field of $`9T`$. We will argue that our increased estimate of $`J_2`$ leads to a larger saturation field and that combined with non-monotonic dependence of Neél temperature on field implies that the experimental results are not anomalous.

Our study of the material Li2VOSiO4 consists of a two band tight-binding model fit to the LDA band structure, which is then mapped onto a Heisenberg model with in-plane ($`J_1`$ and $`J_2`$) and inter-plane ($`J_{}`$) exchange constants. Furthermore, we develop high temperature series expansions and perturbative mean-field theory for the uniform susceptibility and specific heat of the $`J_1J_2`$ model. These allow us to make quantitative comparisons with the experiments.

Li2VOSiO4 crystallizes in the tetragonal system, space group $`P4/nmm`$, containing two formula units per cell with $`a=6.3682`$ Å and $`c=4.449`$ Å. The crystal structure of Li2VOSiO4 is shown in Fig. 1. The magnetically active network of spin half V4+ ions is built up by \[VOSiO4\]2- layers of VO5 square pyramids sharing corners with SiO4 tetrahedra, intercalated with Li ions. The structure of the V4+ square network suggests, that both the nearest neighbor (NN) and the next nearest neighbor (NNN) in-plane coupling should be significant, although it is at best difficult to decide from general considerations which one is dominant. NN coupling is favored by the existence of two exchange channels and shorter distance, NNN coupling profits from the ’straight’ connection between pyramids pointing in the same direction.

In order to obtain a realistic and reliable hopping part of a tight-binding Hamiltonian, band structure calculations were performed using the full-potential nonorthogonal local-orbital minimum-basis scheme  within the local density approximation (LDA). In the scalar relativistic calculations we used the exchange and correlation potential of Perdew and Zunger. V($`3s`$,$`3p`$,$`4s`$, $`4p`$, 3$`d`$), O(2$`s`$, 2$`p`$, 3$`d`$), Li(2$`s`$, 2$`p`$) and Si(3$`s`$, 3$`p`$, 3$`d`$) states, respectively, were chosen as the basis set. All lower lying states were treated as core states. The inclusion of V (3$`s`$,3$`p`$) states in the valence states was necessary to account for non-negligible core-core overlaps. The O and Si 3$`d`$ as well as the Li 2$`p`$ states were taken into account to increase the completeness of the basis set. The spatial extension of the basis orbitals, controlled by a confining potential  $`(r/r_0)^4`$, was optimized to minimize the total energy.

The results of the paramagnetic calculation (see Fig. 2) show a valence band complex of about 10 eV width with two bands crossing the Fermi level. These two bands, due to the two V per cell, are well separated by a gap of about 3 eV from the rest of the valence band complex and show mainly V 3$`d_{xy}`$ and minor O(2) 2$`p_{x,y}`$ character (oxygens of the basal plane of the VO5 pyramid) in the analysis of the corresponding orbital-resolved partial densities of states (not shown). The valence bands below the gap and above the Fermi level have almost pure oxygen and vanadium character, respectively. The contribution of Li and Si states is negligible in the energy region shown.

The relatively narrow bands at the Fermi level (see Fig. 2, lower panel) are half-filled. Therefore, strong correlation effects can be expected which explain the experimentally observed insulating ground state. Because the low-lying magnetic excitations involve only those orbitals with unpaired spins corresponding to the half-filled bands, we restrict ourselves to a two band tight-binding analysis and the discussion of these half-filled bands.

The dispersion of these bands (see Fig. 2, lower panel) has been analyzed in terms of NN transfer $`t_1`$ and NNN transfer $`t_2`$ within the  plane (see Fig. 1 lower panel) and NN hopping $`t_{}`$ between neighboring planes.

Then, the corresponding dispersion relation of the related 2$`\times `$2 problem takes the form

$`E(\stackrel{}{k})`$ $`=`$ $`\epsilon _0+2t_2[\mathrm{cos}(x)+\mathrm{cos}(y)]`$ (2)
$`\pm 4t_1\mathrm{cos}(x/2)\mathrm{cos}(y/2)+2t_{}\mathrm{cos}(z),`$
where $`x=k_za`$, $`y=k_yb`$, $`z=k_zc`$.

The assignment of the parameters has been achieved by two numerically independent procedures: By straightforward least square fitting of the two bands in all directions and by using the energy eigenvalues at different selected high symmetry points. The results are shown in Table I. The errors can be estimated about 5% for the in-plane transfers and 15% for the inter-plane term from the differences of both mentioned above fitting procedures. These small differences can be ascribed to the influence of higher neighbors. The very good agreement of the tight binding fit with the LDA bands justifies a posteriori the restriction to NN and NNN couplings only.      $`t_1`$ (meV) $`t_2`$ (meV) $`t_{}`$ (meV) $`U`$ (eV) $`J_1`$ (K) $`J_2`$ (K) $`J_{}`$(K)    8.5 29.1 -4.8 4 0.83 9.81 0.27     5 0.67 7.85 0.22   TABLE I.:  Transfer integrals of the two-band tight-binding model and the corresponding exchange couplings for different values of the Hubbard $`U`$.   The resulting transfer integrals enable us to estimate the relevant exchange couplings, crucial for the derivation and examination of magnetic model Hamiltonians of the spin-1/2 Heisenberg type:

$$H_{spin}=\underset{ij}{}J_{ij}\stackrel{}{S_i}\stackrel{}{S_j}.$$
(3)
In general, the total exchange $`J`$ can be divided into an antiferromagnetic and a ferromagnetic contribution $`J`$ = $`J^{AFM}+J^{FM}`$. In the strongly correlated limit, valid for typical vanadates, the former can be calculated in terms of the one-band extended Hubbard model $`J_i^{AFM}`$ = $`4t_i^2/(UV_i)`$. The index $`i`$ corresponds to NN and NNN, $`U`$ is the on-site Coulomb repulsion and $`V_i`$ is the inter-site Coulomb interaction. Considering the fact that the VO5 pyramids are not directly connected, but via SiO4 tetrahedra, ferromagnetic contributions $`J^{FM}`$ are expected to be small. For the same reason, the inter-site Coulomb interactions Vi should be small compared with the on-site repulsion $`U`$. From LDA-DMFT(QMC) studies and by fitting spectroscopic data to model calculations, $`U4`$$`5`$ eV is estimated for typical vanadates. Therefore, we adopt $`U`$=$`4`$ eV and $`U`$=$`5`$ eV as representative values to estimate the exchange constants and their sensitivity to $`U`$. The calculated values for the exchange integrals are given in Table I.

Comparing our calculated exchange couplings with the experimental findings, we find excellent agreement for the sum $`J_1+J_2=9.5\pm 1.5`$ K  of the in-plane couplings, reported from susceptibility data to be $`J_1+J_2=8.2\pm 1`$ K. In contrast, we find a ratio $`J_2/J_112`$ which exceeds the experimentally derived ratio in Ref.  $`J_2/J_11.1\pm 0.1`$ by an order of magnitude.

In order to understand the experiments better, we turn to high temperature expansions for the susceptibility and specific heat of the Heisenberg models. Using series expansions ($`T`$=0) , non-linear sigma model theory  (very low-$`T`$), quantum Monte Carlo (QMC) simulations (low-$`T`$)  and high temperature expansions(HTE) (high-T) , the susceptibility of the nearest-neighbor model ($`J_1=0`$) is known accurately for all $`T`$. Letting $`J_2=1`$ and treating $`J_1`$ perturbatively, analogous to chain mean-field theories, leads to the expression

$$\chi (J_1,T)=\chi _0(T)[14J_1\chi _0(T)]$$
(4)
where $`\chi _0`$ is the susceptibility for the Heisenberg model ($`J_1=0`$). As shown in the inset of Fig. 3, at $`T=0`$ for small $`J_1/J_2`$, this expression compares very well with the susceptibility calculated from Ising series expansions. Fig. 3 also shows that applying Eq. 3 to the finite-$`T`$ QMC data for $`\chi _0`$ leads to susceptibility values which join smoothly with the high-temperature expansion results. Thus, we have accurate calculations for the susceptibility of the model with small $`J_1/J_2`$ at all $`T`$.

Rather than find a fit for the exchange constants, in Fig. 3 we show the susceptibility with $`g=2`$; $`J_2=9K`$; and $`J_1/J_2=0,0.1`$ and $`0.2`$. The results are close to experimental values . We note that the agreement will be improved by going to the lower limit of the calculated exchange constants and slightly larger $`g`$-values.

The specific heat data was the primary source for the $`J_1/J_21`$ conclusion by Melzi et al. . They found that the peak value of the specific heat in Li2VOSiO4 was $`0.436(4)R`$ at $`T^m=3.5(1)`$. We find that for the pure Heisenberg model the specific heat peaks at $`T^m=0.60(4)J`$ with a peak value of $`0.455(10)R`$, in agreement with Ref. . With small $`J_1/J_2`$ the peak shifts to lower temperature and the specific heat becomes flatter. The fact that the values for the pure Heisenberg model are close to the experiments strongly favors a small $`J_1`$.

One of the most puzzling aspects of the experimental results is the small moment of 0.24 $`\mu _B`$ at $`T=0`$, obtained from the NMR split patterns. In contrast, the moment of the square-lattice Heisenberg model is well known to be $`0.6\mu _B`$. Taking into account the considerable antiferromagnetic inter-plane coupling $`J_{}`$ resulting from our calculation, a part of the discrepancy could be understood: The Li nuclei sit off-center between two planes, which results in a partial cancellation of the hyperfine fields from antiferromagnetically ordered NN and NNN V sites in neighboring planes (see Fig. 4). This partial cancellation does not change the arguments of Melzi et al. for the pattern of line-splitting (including intensities) and its relation to columnar order because the ordering pattern inside the planes remains the same. However, it leads to a reduction in the effective hyperfine coupling and hence to an enhancement of magnetic moment derived from the line shift. Taking into account the calculated two center overlap integrals for Li and NN and NNN V 3d orbitals, respectively, (see Fig. 4) a crude estimate from Slater-Koster integrals suggests that the NMR split would be reduced by an additional factor of about 2. This results in a moment of about 0.5 $`\mu _B`$ much closer to the value expected for the 2D Heisenberg model.

We now turn to the inter-plane couplings and the measurements of the Neél temperature, $`T_N`$. Applying the expression $`T_N0.36J_{}\xi ^2(T_N)`$  ($`\xi `$ is the in-plane correlation length), to our calculated exchange constants, leads to the estimate $`T_N3.6\pm 0.4`$ K, which is remarkably close to the experimental value of $`2.8`$ K. Furthermore, the saturation field for our calculated exchange constants is about 30 T, which is much bigger than the 9 T field applied by Melzi et al. The Neél temperature should go to zero at the saturation field. However, we note that due to suppression of spin fluctuation the Neél temperature can increase slightly with field, as happens in the purely 2D model. Thus, the experimental result of very weak field dependence of the Neél temperature up to 9 Tesla is consistent with our expectations. The appreciable but still small 3D couplings should also give rise to 3D critical behavior at the finite temperature transition with strong crossover effects. These results on the field dependence of the Neél temperature and the critical behavior at the transition in weakly coupled Heisenberg systems deserve further theoretical attention.

To summarize, we have used LDA to calculate exchange constants for the material Li2VOSiO4 and developed numerical studies for the Heisenberg model to show remarkable consistency with many experimental properties. Electronic structure calculations on the closely related material Li2VOGeO4 will be presented in a forthcoming publication. The key differences are the considerably smaller $`J_2/J_1`$ ratio and coupling to higher neighbors in Li2VOGeO4. Finally, we note that both these materials have a substantial 3D coupling, which leads to long-range order at finite T. It would be interesting to find a material with large-$`J_2`$ that was nearly 2D, thus closer to exhibiting purely quantum order by disorder.

We thank F. Mila and P. Carretta for discussions. This work was supported by the DAAD (individual grant H.R.), the NSF DMR-9802076 and DMR-9986948, the Deutsche Forschungsgemeinschaft, and by the Australian Research Council.