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# Mn 𝐾-edge XANES studies of La1-xAxMnO3 systems (A = Ca, Ba, Pb)

## I Introduction

The La1-xAxMnO3+δ systems exhibit a wide range of different phenomena depending on the concentration, x, of the divalent substitutional atom, A (A = Ca, Ba, Sr, Pb, etc.) and the O concentration. These include ferromagnetism, antiferromagnetism, charge ordering, a metal-insulator transition, and large magnetoresistance effects. For x roughly in the range 0.2-0.5, these systems have a ferromagnetic transition at a transition temperature, Tc, a metal/insulator transition (MI) at T=TMI, and a ”colossal” magnetoresistance (CMR) which reaches it’s maximum at TMR, with TMI $``$ TMR $``$ Tc in many cases. The substitution of a divalent ion for La+3 formally changes the average Mn valence to 3+x (the Mn valence is +3 in LaMnO3 +4 in CaMnO3), and is usually thought to introduce holes into the narrow eg band of Mn 3d-electrons, which are also hybridized with O 2p states. It is the changing occupation of this hybridized band with x that leads to many of the observed properties. Excess O in LaMnO3+δ (actually Mn and La vacancies) or La vacancies can also increase the formal Mn valence, thereby adding carriers to the system.

The coupling between charge and magnetism has been modeled using the double exchange (DE) mechanism plus strong electron-phonon coupling. In the ferromagnetic metallic (FM) state, well below Tc, the charge carriers are assumed to be highly delocalized (large polarons) and spread out over several unit cells for CMR samples.

In the paramagnetic (PM) state above Tc for CMR samples, there is a significant increase in the distortions about the Mn atoms compared to the low temperature data. It is generally assumed that this distortion is a result of the charge carriers becoming localized on the Mn atoms. However, mobile holes could also be located more on the O atoms as is the case for cuprates. Consequently, there might be very little change in the charge localized on the Mn atoms above and below Tc. This raises the question as to how the energy shift of the absorption edge relates to valence and the local environment in these materials. Is there a mixture of “ionic-like” +3 and +4 states, an average valence, as in a metal where all Mn atoms are equivalent, or something in between?

Experimentally, the Mn $`K`$-edge absorption for the Ca substituted manganites is sharp with relatively little structure, and shifts almost uniformly with dopant concentration, consistent with an average valence state of v = 3+x. The sharpness of the edge is suggestive of a transition into a state that is uniform throughout the sample, and initially we interpreted this result to mean that all Mn sites have comparable local charge densities. This is difficult to reconcile with the usual assumption of a mixture of purely local ionic Mn+3 and Mn+4 sites. For example, below we show explicitly that the observed $`K`$-edge cannot be modeled as a weighted sum of the edges of the end compounds LaMnO3 and CaMnO3 for the charge ordered (CO) material with 65% Ca. Note however that even with similar charge densities, the d-electron wavefunctions and the local environment need not be identical at each site. In addition, Tyson et al. have investigated the Kβ emission which probes Mn 3d states through the 3p-1s decay, and report that these spectra for the substituted manganite materials can be modeled as a weighted sum of the end compounds although the shifts with valence are small.

The pre-edge structure for the Mn $`K`$-edge consists of 2-3 small peaks labeled A1-A3 which have Mn 3d character. These features are observed for all the transition metals and are generally ascribed to mixture of 1s-3d quadrupole and 1s-p dipole transitions (made weakly allowed by a hybridization between 3d states and p-states). Although the latter are assumed to be dominant, the interpretation of the Ai peaks is still controversial. Two important issues are: 1) How large is the quadrupole contribution and when is it important? and 2) How are the dipole transitions made allowed since in many instances, the local environment has inversion symmetry, and in that case, the transition is symmetry forbidden? There have been a large number of papers in the last five years addressing these issues for many of the transition metals, not all of which are in agreement. However some questions have been answered. Since quadrupole-allowed pre-edge features have a strong angular dependence, in contrast to the dipole-allowed transitions, measurements on single crystals, as a function of angle can separate the two contributions. Such studies have shown that quadrupole transitions contribute to the Ai peaks in Ti, V, Ni, and Fe, with the largest contribution at the lowest energies of the pre-edge. The amplitude can be as large as $``$ 4% of the absorption edge height for some systems at optimum orientations; but more generally it is of order 1%, and could be smaller in powdered samples which are orientational averages. The dipole-allowed Ai peaks are often in the 5-15% range and often do dominate, but not always. For example, for Ti in rutile (TiO2), the small A1 peak appears to be primarily a quadrupole feature.

Early Mn XANES work assumed that the A1-A2 splitting is produced by the crystal field parameter, often called the 10Dq parameter, which splits the t2g and eg states. These investigations did not consider the possibility of a large on-site Coulomb term, U. Recent work, using the Local Spin Density Approximation (LSDA or sometimes LDA) with and without U, and including the Hund’s rule exchange parameter, JH, find a Coulomb splitting of both the t2g and eg states, with the eg states further split by the Jahn-Teller (J-T)interaction.

Pickett et al, (LSDA model) suggest that these systems are half metallic, with a gap between the O band and a minority spin d-band. They also point out that near 25 % Ca, all Mn sites could be essentially identical if the Ca were uniformly distributed such that there are two Ca and six La second neighbors to each Mn. Thus for the concentration range 20-30%, the local environment for each Mn may be very similar. Anisimov et al. and Mizokawa et al. suggest that a large fraction of the d-electrons are found on the Mn atoms rather than being transferred to the O atom as in an ionic solid (thereby leaving holes in the O band). These calculations yield nearly the same electron density on each Mn atom, for sites associated with formal Mn+3 and Mn+4 valences. Other recent papers have also stressed the importance of O, and the question of charge localization on the O atoms or on the Mn atoms has been considered.

Some promising calculations for considering the pre-edge features are those of Elfimov et al. These calculations indicate that in addition to U and JH, there are appreciable higher order Coulomb terms that must be included and that strong hybridization occurs between the Mn 4p orbitals and the Mn 3d states on neighboring Mn atoms. The resulting splitting of the majority and minority eg spin states results in a splitting of the Mn pre-edge features. We consider these calculations together with some of the new results on pre-edges in the discussion section.

In this paper we address the valence question and probe the Mn 3d bands using the near edge structure. Specifically we show there is no Mn $`K`$-edge shift (within 0.04 eV) through Tc. We also compare the main edge, which is too narrow to arise from a mixture of ionic Mn+3 and Mn+4, with the edge for a material, Sr3Mn2O6.55, that does have a mixture of these ions. In addition, using a careful subtraction method, we show that there is indeed a small structure in the main edge that correlates with Tc for the CMR samples and with TCO for the charge ordered material. The structure for CMR material is out of phase with that for the CO sample - which suggests that there is a distortion for the CO sample that increases at low T. We also note that the pre-edge structure has a temperature dependence which again correlates with Tc for CMR samples. The splitting of the pre-edge peaks decreases in the ferromagnetic phase which may indicate a change in covalency. Finally our interpretation of the XANES differs from earlier work on Mn $`K`$-edges but is consistent with recent studies of other transition metal atoms.

In Sec II we summarize the samples and experimental setup; some details were given earlier. Then in Sec III, we provide a more extensive discussion of the shift of the Mn $`K`$-edge as a function of concentration and temperature. Here we also present the pre-edge results. We consider the implications of these results in Sec IV.

## II Experimental details

Many samples are used in this study, with the average Mn valence changed in a variety of ways:- divalent substitutions for La+3 and changes in the La+3 or O concentrations. Powder samples of La1-xAxMnO3 were prepared by solid state reaction of La2O3, MnO2, and a dopant compound - CaCO3, PbO, BaO, for various divalent atoms, A. Ca substitutions are $`x`$=0.0, 0.12, 0.21, 0.25, 0.3, 0.65 and 1.0, and Ba and Pb are 0.33. Several firings with repeated grindings were carried out using temperatures up to 1400C, with in some cases a final slow cool at 1C per minute. The dc magnetization was measured using a commercial SQUID magnetometer. The end compounds, CaMnO3 and LaMnO3.006, show antiferromagnetic transitions at $``$130 and 125 K, respectively, while the $`x`$=0.65 sample showed features consistent with a charge ordered (CO) transition at 270 K and an AF transition at$``$140 K. Similar measurements on the substituted manganites indicates that they are all orthorhombic. The average Mn valence for several Ca substituted samples was also determined by titration (Sec. III A). See Refs.  for further details.

The LaMnO3.006 sample was prepared by grinding stoichiometric amounts of La2O3 (Alfa Aesar Reacton 99.99%) and MnO2 (Alfa Aesar Puratronic 99.999%) in an Al2O3 mortar and pestle under acetone until well mixed. The powder sample was formed into a 3/4” diameter pellet using uniaxially presure (1000lbs), and fired in an Al2O3 boat under pure oxygen for 12 hours at 1200-1250C. Next the sample was cooled to 800C, re-ground, re-pelletized, and refired at 1200-1250C for an additional 24 hours. This process was repeated until a single phase, rhombohedral XRD trace was obtained. The reground powder was placed in an Al2O3 boat and post-annealed in UHP Ar at 1000C for 24 hrs. The oxygen partial pressure was about 60 ppm (determined using an Ametek oxygen analyzer). The sample was then quenched to room temperature. Diffraction, titration and TGA measurements indicate this sample is essentially stoichiometric, with an oxygen content of 3.006.

Additional LaMnO3+y specimens with various average Mn valences were prepared at 1300 C in air, followed by three intermediate regrindings. The original specimen was removed from the furnace at 1300 C and has a Mn valence of 3.150. A piece of this specimen was reacted overnight at 1000 C and removed from the furnace, producing a sample with an average Mn valence of 3.206. A nearly stoichiometric specimen with average Mn valence of 3.063 was prepared at temperatures up to 1350 C with 4 intermediate regrindings in flowing helium gas. Finally, the nonstoichiometric La0.9MnO3 specimen was prepared at temperatures of up to 1350 C with three intermediate regrindings. It was slow-cooled in air at 1.5 C/min to room temperature and had an average Mn valence of 3.312. For each of these samples the valence was determined by titration.

A sample that should have isolated Mn+3 and Mn+4 species is also needed for comparison purposes; such a material is Sr3Mn2O6.55. The two species are due to the oxygen defect structure that puts vacancies into the MnO2 planes to form mixtures of square pyramids and octahedra. This highly insulating material can then be understood from chemical reasoning to be Mn+3 (square pyramids) and Mn+4 (octahedra). Some further justification for this assignment comes from the compound Ca2MnO3.5, which is all Mn+3 and has only square pyramids with vacancies in the MnO2 planes; it is an ordered superstructure of the single-layer compound. Sr3Mn2O6.55 was synthesized by firing a stoichiometric mixture of SrCO3 and MnO2 at 1650 C for 12 hr followed by rapid quenching into dry ice. This procedure is essential to prevent decomposition into $`\alpha `$-Sr2MnO4 and Sr4Mn3O10 on cooling and to prevent oxidation to Sr3Mn2O7. The oxygen content was measured independently by iodometric titration and by thermogravimetric analysis, both techniques yielding 6.55(1) oxygen atoms per formula unit.

All XAFS data were collected at the Stanford Synchrotron Radiation Laboratory (SSRL). Most Mn $`K`$-edge data were collected on beam line 2-3 using Si(220) double monochromator crystals for all samples. Some data were collected on beam line 4-3 using Si(111) crystals, while most of the Mn $`K`$-edge data for the Ba substituted sample were collected on beam line 10-2 using Si (111). The manganite powders were reground, passed through a 400-mesh sieve, and brushed onto scotch tape. Layers of tape were stacked to obtain absorption lengths $`\mu _{\mathrm{Mn}}t`$1 ($`\mu _{\mathrm{Mn}}`$ is the Mn contribution to the absorption coefficient and $`t`$ the sample thickness) for each sample. Samples were placed in an Oxford LHe flow cryostat, and temperatures were regulated to within 0.1 K. All data were collected in transmission mode. A powdered Mn metal sample was used as an energy reference for each scan. The pre-edge absorption (absorption from other excitations) was removed by fitting the data to a Victoreen formula, and a simple cubic spline (7 knots at constant intervals $``$140 eV in $`E`$) was used to simulate the embedded-atom absorption, $`\mu _0`$, above the edge.

The edge shifts are reported relative to a Mn powdered metal foil for which we take the position of the first inflection point to be 6537.4 eV. For each scan, the position of the reference edge was determined by fitting the edge to that of a fiducial scan. This provided a correction to the relative edge position consistent within $`\pm `$ 0.015 eV - see next section.

In the pre-edge region there is a remnant of the La LI XAFS that must be considered; the oscillation amplitude is about 0.3 % of the Mn step height, just before the pre-edge. However, the La $`K`$-edge XAFS show that there is a ”beat” in the XAFS from about 8.4-10 Å-1, which for the La LI XAFS corresponds to the range of the Mn XANES. In this beat region the La LI XAFS is reduce by another factor of 4; thus the La oscillations underlying the Mn XANES region has an amplitude of about 0.08%, much smaller than the changes we investigate. In addition, this oscillation is slowly varying with energy, and would at most produce a slowly varying background. Consequently any remaining La LI XAFS are not a problem for the Mn XANES study.

## III Near edge results

### A Main edge

In Fig. 1 we show the Mn absorption $`K`$-edge for several concentrations of Ca, 33% Ba and Pb, La0.35Pr0.35Ca0.3MnO3, a Sr3Mn2O6.55 sample that should have a nearly uniform mixture of ionic Mn+3 and Mn+4, some O excess samples, and a La deficient sample.

For the Ca substituted samples several points are immediately obvious: (1) To first order the main absorption edges (ignoring pre-edge structures for now) have almost the same shape for each dopant concentration and shift nearly rigidly to higher energy as the concentration is increased, (2) the edges for the manganite samples are very sharp, roughly half as wide as the edge for the Sr3M2nO6.55 sample, (3) there is no obvious kink or structure in the sharp edges for the substituted (La,Ca) manganite samples that would indicate a simple mixture of Mn+3 and Mn+4 ions, (4) however, there is a tiny shape change, visible in Fig. 1 for samples of different concentration, which shifts the position of the inflection point on the edge relative to the half height position.

The data for the La0.35Pr0.35Ca0.3MnO3 sample looks very similar to that for La0.7Ca0.3MnO3 indicating that replacing some of the La by Pr does not change the local electronic configuration on the Mn. The O excess and La deficient samples show a similar edge shape to LaMnO3, but the edge shift is considerably smaller than expected based on the Mn valence obtained from TGA. The shifts for the O excess data are inconsistent with data from other groups and are included here to show the sharpness of the edge. However, such data suggest that the position of the Mn $`K`$-edge is determined by several factors and using the Mn valence and O content obtained from TGA may not be sufficient.

In contrast to the Ca substituted materials, Ba and Pb substitution results in a significantly broader edge, more comparable to the edges of other Mn oxides and the Sr3Mn2O6.55 sample. There is relatively more weight in the lower part of the edge.

In addition to the shift of the inflection point position on the edge with Ca concentration, as noted above, the region of steepest slope is also quite broad. Consequently using the position of the peak in the first derivative curve as a measure of the average edge position (as we and others have done previously) is only an approximate measure of the average edge shift. Using the derivative peak yields a roughly linear shift with concentration. Our data and that of Subías et al. have the same edge shift per valence unit, while the shift reported by Croft et al. is smaller. This may be the result of different O content in the samples.

To obtain a better estimate of the average edge shift with concentration (at room temperature), we have fit the LaMnO3 edge data (or the CaMnO3 data) to that for each of the other samples, over the main part of the edge (above the pre-edge structure). In this procedure it is important that when the absorption from other atoms is removed, the data base-line below the pre-edge structure be at zero. Each edge is also normalized using some feature of the data; for the data at different concentrations, we normalized over a range of energies well above the edge, where the XAFS oscillations are small. Similarly we fit the corresponding reference edges (Mn foil) to a reference scan to obtain a net overall edge shift. Several examples of these fits are shown in Fig. 2. Although there is a change in shape between LaMnO3 and CaMnO3, the relative shifts determined with either end compound are nearly identical - less than 0.02 eV difference over the entire concentration range.

In Fig. 3a we plot the relative shifts obtained from fits to LaMnO3 at room temperature. The shift with x is roughly linear with concentration, with a net shift from 0 to 100% Ca of $``$3 eV. This is considerably smaller than the value 4.2 obtained from the derivative peak and illustrates the effect of the shift of the inflection point relative to the half height. However, over the straight part of the plot from x= 0.3-1.0, the slope is 3.3 eV/valence unit, quite close to the 3.5 eV/valence unit obtained by Ressler et al. for MnO, Mn2O3, and MnO2. The point at x = 0.12 is anomalous, but titration measurements give about the same Mn valence for the 12 and 21% samples, which agrees with the comparable edge shifts. The same data is re-plotted as a function of the titrated valence in Fig. 3b; in this case the variation with valence is smoother, but slightly non-linear. The different values for the titrated valence, compared to the value expected from the Ca concentration may indicate that there are slight variations in O content in some samples.

We have also used a similar analysis to investigate any possible edge shift as a function of temperature, by fitting the entire edge of the 50K data for a given sample to all the higher temperature data files. Two examples are shown in Fig. 2c,d. This figure shows that changes in the shape of the main edge, above and below Tc, are quite small (although measurable). The largest relative change is in the pre-edge peaks, to be discussed later. In Fig. 4 we show the shift of the edge position as a function of temperature up to 320K for several sets of samples. (We have similar data out to nearly 500K for the Ba sample and CaMnO3.) Variations in the fit values for the net shift, $`\mathrm{\Delta }`$Eo, for several traces at the same temperature are less than $`\pm `$ 0.02 eV, and fluctuations about the small average shift with T are comparable for a given experimental run. Differences between experimental set-ups or using Si$`<`$111$`>`$ or Si$`<`$220$`>`$ monochromators are less than 0.1 eV. For T less than 300K, the net shift for each sample is very small (less than 0.04 eV), but nearly all appear to have a slight decrease at high T.

### B Pre-edge region

In Fig. 5 we plot the pre-edge region as a function of temperature on an expanded scale for CaMnO3, a CMR sample with 21% Ca, and the 33% Ba sample. Data for LaMnO3, the CO sample with 65% Ca and another CMR sample have recently been published in a short paper. For these systems the main features are the lower three peaks labeled A1-A3 (near 6539, 6541, and 6544 eV) and the B peak. The lower two peaks A1 and A2 are common to all materials although not resolved for the 33% Ba data collected using Si (111) crystals which have a lower energy resolution. The comparison of the two Ba data sets in this figure illustrate the importance of using high energy resolution. The A3 peak is not obviously present in most samples. In Fig. 6 we compare the data for the 30% Ca CMR sample with the Sr3Mn2O6.55 sample and also show the pre-edge for the Pb sample, all on a more expanded scale.

There are several features to note; all the pre-edge features start at very nearly the same position regardless of doping and the amplitude of the pre-edge features labeled A increases with average Mn valence (Ca concentration) as observed in other Mn compounds and in a previous manganite study. There are, however, small shifts of these features with Ca concentration as shown in Fig. 7. The A1 peak energy increases slightly from LaMnO3 to CaMnO3, and the A1-A2 splitting decreases from 2.2 to 1.8 eV. (The exception is the 65% sample, but here the Ai peaks are poorly resolved.) For the substituted samples, the leading edge of the A1 peak remains steep for all concentrations except the 65 % sample. Consequently, the pre-edge for the intermediate concentrations (CMR samples) cannot be modeled as a simple weighted sum of the end compounds LaMnO3 and CaMnO3. Note that the leading edge for the Sr3Mn2O6.55 sample (See Fig. 6) is broader, consistent with a mixture of Mn+3 and Mn+4 ions, and also has a significant A3 peak. The latter is not present in the data for 30% Ca.

The Ba and Pb pre-edges are slightly different; the Ba pre-edge features are not as well resolved even for the higher energy resolution data while the A1 peak is largest for the Pb sample (Compare Fig. 6 with Fig. 5).

The most striking feature in Figs. 5,6 is the variation in the intensity of the pre-edge peaks and the shift of A2 as T increases through Tc for the CMR samples. In contrast, the change for LaMnO3 is small up to 300K. For the 21% Ca sample in Fig. 5 the A1 peak decreases in amplitude while the A2 and B-peaks increase with increasing T; the A2 peak is sharpest at 300K and clearly shifts downward below Tc (0.4 - 0.5 eV, depending on the background function used). See the solid triangles in Fig. 7. The change in the A-peaks for the 33% Ba sample (using the high resolution monochromator) appear to follow the same trend as observed for the Ca data (Fig. 6) but the A2 peak is not as well resolved.

The largest temperature dependence is observed for the CaMnO3 sample above 300K (See Fig. 5a), with the largest increase occurring for the B-peak. Also, the amplitude of the peak at the top of the edge, commonly called the “white line”, (see Fig 1c at 6554 eV for example) decreases slightly at high T. These effects become much larger at only slightly higher temperatures and will be treated in a separate paper. For the CMR samples, we associate the temperature dependent changes in the amplitude of the pre-edge features with changes in charge localization/hybridization.

### C Difference Spectra

More detailed information can be obtained by examining the change in the shape of the XANES region as a function of temperature. The files are first shifted to correct for any small changes in the energy of the monochromator and all spectra are carefully normalized as discussed earlier. The difference spectra are obtained by subtracting the data at 300K from all the data files (at different temperatures) for a given sample. This approach was used originally to investigate the pre-edge region for the 21% sample, but considerable structure was found at energies corresponding to the main edge, for both the CMR and CO (x=0.65) samples. Several examples of these difference spectra are shown in Fig. 8 for LaMnO3, CaMnO3, and the 21, 30, and 65 % Ca substituted samples.

In the pre-edge region, the temperature variation of the A1 and A2 peaks for the 21 and 30% Ca (CMR) samples is very clearly visible in Fig. 8c,d; it begins at Tc, with most of the change occurring over a 60K range just below Tc. The temperature-dependent changes of the pre-edge are comparable in both samples, with the magnitude of the change of the A2 peak being roughly 50-70% that of the A1 peak. For the 65% Ca sample, changes of the Ai with T are also observed in the different spectra, but the amplitudes are considerably smaller, and interestingly, the phase is inverted - the A1 difference peak decreases instead of increasing. For the LaMnO3 sample (Fig. 8a) there is essentially no structure in the difference spectra over the pre-edge energy range, but surprisingly there are small peaks in this range for CaMnO3 (See lower part of Fig. 8a), with the largest peak in the difference spectra occurring between A2 and A3 \- this suggests that there are in reality more than three pre-edge peaks.

There is also well defined structure in the difference spectra over the energy range of the main edge, although it is only a few percent of the edge in amplitude. For LaMnO3 there is a broad feature over most of the edge region which increases as T is lowered. CaMnO3 has a similar feature but it is larger and narrower (Fig. 8a). Both appear to correspond to the temperature dependent peak near the top of the edge (the “white line” mentioned earlier) which is sharpest at low T. For the CMR samples, there is additional structure on top of this broad peak - a dip at 6551 and a peak at 6553 eV (2 eV apart). Another dip/peak occurs just above the edge at 6555-6556.5 eV. The CO sample also shows structure over this energy range but again the phase is inverted relative to the CMR samples (i.e. a peak/dip at 6552 and6554 eV), \- this phase inversion thus extends over the entire near-edge region.

## IV Discussion

### A Main edge

For Mn atoms the main $`K`$-absorption edge represents transitions mainly from the atomic 1s state to the empty Mn 4p band. The XANES results show that this edge is very sharp for the Ca-substituted samples, the O-excess samples and the La deficient sample. The width of the edge (roughly 5-6 eV) is narrower than the edge for most other Mn compounds and the shift in edge position is $``$ 3 eV for a valence change of +1. No obvious indication of a step or double edge structure is present that would indicate two distinct valence states. If completely localized Mn+3 and Mn+4 ions were present on time scales of 10-14 sec, the edge should have a smaller average slope and generally be broader, as would be expected for a mixture of fine powder of LaMnO3 and CaMnO3. To model this explicitly, we compare in Fig. 9 the experimental edge for the 65% Ca (CO) sample and a weighted sum of the +3 and +4 end compounds; clearly the experimental edge is much sharper as noted previously.

In contrast to the Ca-doped samples, the edge for Sr3Mn2O6.55 is much broader (Fig. 1a), with a width of 10-12 eV. There is also a change of slope of the main edge for this sample that is consistent with two valence states, but the shape is more complicated. Note that a combination of two edges each $``$5 eV wide, separated by $``$3 eV (the separation for a valence change of 1) would yield an edge of width $``$ 13eV. Thus the width and structure of the Sr3Mn2O6.55 edge are both consistent with the expectation that two valence states are present in this sample – Mn+3 and Mn+4. Similarly our data for Mn3O4, which has a mixture of +2 and +3 valence states, has a very broad edge of 13-14 eV (not shown).

The edges for the Ba and Pb samples are also broader; they have a break in slope and more amplitude in the lower part of the edge that might suggest two valence states. In this regard they are quite different from the Ca substituted samples for which the shape of the main edge for the CMR samples does not change much from that of LaMnO3. In addition, the net shifts of the edges for the 33% Ba, and Pb samples are smaller than expected; the additional structure near 6546-48 eV shifts the lower part of the edge down in energy while the top of the edge is close to the position of the 30% Ca samples. The net result is a very small overall average edge-shift compared to LaMnO3.

We have also shown by fitting over most of the edge, that there is no significant change in the average edge position for any of the substituted manganite samples near Tc. This agrees with our earlier result in which we averaged data points above and below Tc. The new analysis also indicates that there is consistently a slight decrease in edge position at the highest temperatures, that is largest for CaMnO3 and Sr3Mn2O6.55. The reason for this downward shift is not yet clear but may be related to the temperature dependence of the B peak (since an increase in the B-peak intensity effectively shifts the lower section of the edge to lower energy).

However, the lack of any temperature dependence below Tc disagrees with the earlier work of Subías et al., who report a 0.1 eV decrease in edge position up to Tc for La0.6Y0.07Ca0.33MnO3 and then a 0.09 eV increase up to 210K. The small but important change in the shape of the main edge in Fig. 8 provides a partial explanation for this discrepancy. Subías et al. assumed no change in edge shape and calculated difference spectra for each temperature. Under this assumption, the amplitude of the peak in the difference spectra would be proportional to the energy shift of the edge. The additional structure observed in the difference spectra indicates there is a shape change rather than an overall edge shift.

The difference spectra (Fig. 8) also show clearly that the additional structure is dependent on Tc. For the CMR samples, the dip-peak structure, superimposed on the peak observed for the end compounds, begins to be observable near Tc and grows rapidly in the 60-100K range just below Tc. This structure means that compared to the edge at low temperatures (undistorted Mn-O bonds) the edge above Tc (distorted Mn-O bonds) has the upper part of the edge shifted upward in energy while the lower part is shifted downwards. The separation between the dip-peak structure is about 2 eV (see vertical dotted lines).

This raises several questions - for the CMR samples is there a mixture of +3 and +4 sites as usually assumed? If so why is the edge structure so small? Can the small structure observed in the difference spectra be explained in some other way? One aspect that must be included is the very large width of the Mn 4p density of states (DOS), roughly 15 eV wide, that is found in two quite different recent calculations. The main edge is due to transitions into this band and the calculated absorption edge (broadened by the core-hole lifetime) is very similar to that observed experimentally. The broad width means that the 4p states are extended and not localized on one Mn atom. Consequently, the $`K`$-edge will correspond to a Mn valence partially averaged over several Mn atoms, and thus will be less sensitive to variations in local charge on different Mn sites.

Another possibility is that the system is more covalent and that there are some partial holes in the O 2p band which is hybridized with the Mn 3d states. This is supported by several calculations and by the observation of holes in the O 2p band in absorption studies. Such holes may play an important role in the unusual transport of these materials. In calculations, Anisimov et al. and Mizokawa and Fujimori obtain two types of Mn eg configurations with almost identical local charge densities. In both calculations there are distortions of the Mn-O bond distances. For the calculation of Anisimov et al., one configuration is symmetric in the $`ab`$ plane with four small equal lobes directed towards O while the other has two large (and two small) lobes, again directed towards O atoms in the $`ab`$ plane. The more symmetric case is associated with a formal Mn+4 site and the other state with Mn+3 but because the charge densities are comparable would not lead to significantly different edge shifts. The recent calculations of Elfimov et al. are also relevant. To fit the observed splittings of Ai peaks (2.2 eV for LaMnO3 and 1.8 eV for CaMnO3), U and JH had to be lowered from the values in the first calculation \- to 4 eV and 0.7 eV, respectively, which implies higher covalency.

The remaining question to be answered about the main edge for the CMR samples is what is the explanation for the small structure in the difference spectra as T is lowered below Tc? A possible answer is again found in the calculations of Elfimov et al.. They find that the position of the 4p partial DOS is bond-length dependent - it occurs at a lower energy when the Mn-O bond lengthens (px orbitals in their paper) and is at a higher energy for shorter bond lengths ((py and pz). Such a shift is expected; in polarized XAFS experiments on high Tc materials we have observed edge shifts between the c- and a-axes. In addition, studies of molecules show that the edge shifts to higher energy when the bond length shortens. The separation between the partial DOS for px and py is about 2 eV in Elfinov etal’s calculation when they use distortions similar to those observed in LaMnO3; we expect to see some evidence of this splitting in the experimental absorption edge, although it is lifetime broadened and the 4p states are extended. We propose that the tiny dip-peak structure observed for the CMR materials is the result of the different positions for the partial DOS for px and py. The dip-peak splitting is also about 2 eV but it is not clear whether this is significant or a coincidence.

For the CO sample there is also structure in the edge but the phase is inverted. If the above explanation for the dip-peak structure in the difference spectra for CMR samples is correct then it suggests that the peak-dip feature for the CO sample is also produced by local distortions - but in this case by a local distortion that starts at the charge ordering temperature, TCO=270K, and increases as T is lowered. Such a model then provides a simple interpretation for the unusual lack of temperature dependence (reported but not explained) for $`\sigma ^2`$ for this sample. The surprise is that at least the thermal phonon broadening should have caused some increase in $`\sigma ^2`$ with T. However, if there is a distortion associated with the CO state, then there must be an associated broadening contribution $`\sigma _{CO}`$, for the Mn-O pair distribution function, $`\sigma _{CO}^2`$, that is zero above TCO and increases as T is lowered below TCO. Then the total variance for the Mn-O bond, $`\sigma _{MnO}^2`$, will be given by

$$\sigma _{MnO}^2(T)=\sigma _{phonon}^2(T)+\sigma _{CO}^2(T)+\sigma _{static}^2$$
(1)
where $`\sigma _{phonon}^2(T)`$ is the phonon contribution, and $`\sigma _{static}^2`$ is a static (temperature-independent) contribution from disorder. $`\sigma _{phonon}^2(T)`$ should be comparable to that for CaMnO3, since we see the same phonon component for both pure CaMnO3 and La0.79Ca0.21MnO3 above Tc. To make $`\sigma _{total}^2`$ nearly independent of T means $`\sigma _{CO}^2(T)`$ and $`\sigma _{phonon}^2(T)`$ almost cancel for temperatures below 300K.

We can extract the CO contribution following the method in Ref.  for calculating $`\mathrm{\Delta }\sigma ^2`$ \- we fit the two highest T data points (from Ref. ) to $`\sigma _{phonon}^2(T)`$ \+ $`\sigma _{static}^2`$ and then subtract these contributions from the data. In Fig. 10 we plot the result of this analysis for the 65% Ca sample. From this figure, the maximum value for $`\sigma _{CO}^2(T)`$, is roughly 10% of that associated with polaron formation for the CMR samples. Such an increased distortion for charge ordered material makes sense \- as the sample becomes charge or orbital ordered, there is more room for the longer Mn-O bonds to lengthen, while for a random arrangement of orbitals, the series of long and short Mn-O bonds are more constrained.

### B Pre-edge region

#### 1 Background

The pre-edge results provide additional information about the nature of the electronic states. For many of the transition elements, 1-3 pre-edge peaks, Ai, occur well below the main edge ($``$ 15eV below) and are assigned to transitions to empty states with d-like character, i.e. these are 1s to 3d(n+1) transitions where n is the initial number of d electrons and n+1 includes the excited electron in the final state, which usually includes the effect of a core hole. The 1s-3d transitions are directly allowed through the very weak quadrupole transition or allowed via an admixture of 3d and 4p states. In the pre-edge region there may also be some hybridization with the O 2p states. If the metal site is centrosymmetric, there is no mixing of 3d and 4p states on the excited atom and 1s-3d dipole transitions are strictly forbidden; however local distortions can make such 1s-3d transitions very weakly dipole allowed. Three aspects need to be recognized in considering the Mn pre-edge in the present study.

* Quadrupole interactions
Although the quadrupole interaction is weak it has a clear signature through the angular dependence of the absorption process. Based on recent studies on oriented single crystals we estimate that quadrupole-allowed peaks will be at most 1% in powder samples which is considerably smaller than the Ai peaks observed for the substituted manganites but perhaps not negligible. A small quadrupole component, as seen for example in FeO, may well be present.
* Dipole allowed via 3d-4p mixing on the absorbing atom
If the Mn site lacks inversion symmetry, then in principle there will be mixing of the Mn 3d and 4p states on the central atom. Consider a system that is nearly cubic but has a small distortion that removes the inversion symmetry - i.e. the metal atom is slightly displaced such that the bonds on opposite sides of the metal atom are slightly different. Then the mixing parameter is $``$ $`\delta _l/r_o`$ and the matrix element will be proportional to $`(\delta _l/r_o)^2`$, where $`\delta _l`$ is the difference in opposite bond lengths and $`r_o`$ is the average bond length. An example is the V site in V2O5; here the VO6 octahedron is strongly distorted, and along the c-axis, the two V-O bond lengths are 1.577 and 2.791 Å respectively. Experimentally there is a large pre-edge peak for the V $`K`$-edge that can be modeled assuming 3d-4p mixing on the absorbing atom plus the effect of a corehole.
* Dipole allowed via 4p mixing with neighboring metal atom 3d states
In several cases, a significant pre-edge peak is observed in a cubic crystal, which can’t be explained by the above 3d-4p mixing on the excited atom. Multi-scattering calculations for such systems often show that large clusters are needed before the pre-edge features are produced - scattering paths are needed which include many further neighbors, particularly the second neighbor metal atoms. An equivalent result emerges from band theory calculations where the hybridization of extended states is important. Here the dipole transition can be made allowed via mixing of the 4p state on the central atom with the 3d states on neighboring atoms. Projections of the density of states with p character (p-DOS) for such systems show small features at the energies of the 3d states; such features are not observed in the p-DOS when the pre-edge feature is a quadrupole transition. In the limit of multi-scattering calculations with very large clusters, the two approaches (band theory and multi-scattering) should be equivalent.

To have a mixing of 3d with the 4p states (to make a state of p-character), one needs a combination of 3d states that has odd parity as pointed out by Elfimov et al.. It is easy to obtain such a state if a linear combination of 3d states on two neighboring Mn atoms is used and the p-states are extended enough to partially overlap them. Specifically, consider 3 Mn atoms in a line - a central excited atom (0) and left (L) and right (R) atoms - with $`\mathrm{\Psi }_{4p}`$(0) being the 4p state on the central atom, and $`\mathrm{\Psi }_{3d;x^2y^2}`$(RR) and $`\mathrm{\Psi }_{3d;x^2y^2}`$(RL) being the 3d$`_{x^2y^2}`$ states centered on the right and left atoms. Then a state with odd symmetry about the central atom is given by

$$\mathrm{\Psi }_{total}=\alpha \mathrm{\Psi }_{4p}(0)+\frac{\beta }{\sqrt{2}}(\mathrm{\Psi }_{3d;x^2y^2}(R_L)\mathrm{\Psi }_{3d;x^2y^2}(R_R))$$
(2)
where $`\alpha `$ is essentially 1.0 and we ignore the intervening O atom via which the hybridization occurs. The small parameter, $`\beta `$, is a measure of the hybridization and is strongly dependent on the overlap of the 4p and 3d wavefunctions on different Mn atoms, and hence on the distance between them.

#### 2 Application to the substituted manganites

The pre-edge for the substituted manganites follows the general trends observed for other Mn systems quite well. Three A-peaks are observed for CaMnO3; A2 is larger than the A1 peak, and the A2-A1 splitting is smaller (high valence - +4) than for other samples. The LaMnO3 case is similar; the A2-A1 splitting is largest (lower valence +3) and the overall A peak amplitude is smallest. However, the A2 peak is larger than expected from the literature for Mn+3 states in other compounds, possibly because of increased local distortions in this compound.

However, there are difficulties with some of the earlier interpretations in which the dipole allowed transitions are assumed to originate from a 3d-4p mixing on the excited atom. First the Ai peaks appear for both distorted and undistorted systems. Second, the amplitude (particularly for the relatively undistorted system CaMnO3) is too large to be a 1s-3d transition made allowed by a slight breaking of inversion symmetry about the excited Mn atom. Recently, based on the calculations of Elfimov et al., we have interpreted A1 and A2 as dipole allowed via a mixing of Mn 4p states with Mn 3d states on neighboring metal atoms. The projected p-DOS in the calculations of Elfimov et al. show two features in the pre-edge region, which indicates that dipole-allowed transitions should be present. In addition, the broad Mn 4p band obtained in that work and by by Benfatto et al., also implies that the 4p states are indeed extended - a necessary requirement for mixing with the 3d states on the neighboring metal atoms. Similar interpretations have been given recently for other transition metal systems that are cubic or very nearly so; Fe in FeO and Ti in rutile. A mixing with the 3d states on neighboring Ti atoms was also reported in the layered disulfide TiS2.

The calculations of Elfimov et al. also show that there is a splitting of the unfilled 3d bands - the lowest is the majority eg band (which may be partially filled via doping); the next two are the minority eg and t2g bands which partially overlap. The coupling with the t2g is expected to be smaller since these orbitals are of the form dxy, which has reduced overlap with the Mn 4p in a $`\pi `$ bonding configuration. The splitting of these eg bands depends both on JH and on the degree of covalency/hybridization. As reported recently, adjusting the parameters in this calculation so that the theoretical splitting is close to the 2 eV observed experimentally, resulted in U=4 eV and JH=0.7 eV. These lower values also suggest an increase in covalency and hence that the charge is shared between Mn and O. Consequently, there is a non-zero density of holes in the O bands, in agreement with Ju et al. and these O-holes may play an important role in the unusual transport of these materials. For the CMR samples, the additional decrease in the A1-A2 splitting for T$`<`$Tc may suggest a further increase in covalency.

Finally the temperature dependence of the Ai peak amplitudes is still not explained. Comparing the pre-edges of distorted LaMnO3 with almost undistorted CaMnO3 (See Fig. 5) would suggest that as the CMR samples change from distorted above Tc to ordered at low T, the A2 peak would increase relative to A1. Experimentally the reverse is true. However, we still suggest that the observed temperature dependence arises from the change in local structure, based on the fact that the changes for the CMR and CO samples are out of phase for both the pre-edge features and the structure in the main edge.

#### 3 Other Models

Another general feature that emerges from our data is that although the main changes occur just below Tc, there is also a gradual change to the fully ordered state as the sample is cooled well below Tc, and the local structure continues to change down to 50K and below. Consequently there may be clusters formed at Tc that grow as T is lowered. We have interpreted our local distortion results earlier in terms of a two component model. Within that model, one of these components (fluids) would correspond to delocalized states - these could be either delocalized holes or delocalized electrons. We also point out that the decreasing distortions observed in EXAFS as T is decreased below Tc and the corresponding increase in resistivity suggest a changing average mobility of the charge carriers. Within the model we have suggested, the fraction of delocalized carriers would increase as T is lowered. However, one of these components might also correspond to the Mn atoms in a cluster, the positions of which are dominated by small variations in dopant concentration or O vacancies, possibly leading to a regime with phase separation. Such inhomogeneities likely play an import role in these materials. In addition, Jaime et al. have successfully modeled their resistivity and thermoelectric measurements using a two component system of localized and itinerant carriers. The recent calculations using the Kondo model also stress phase separation but it is not clear how to compare with their results.

## V Conclusions

We have addressed several issues related to the Mn valence in the substituted LaMnO3 materials. Although discussions of these systems often assume isolated Mn+3 and Mn+4 states, we observe no change ($`<`$ 0.02 eV) in the average edge position through the ferro-magnetic transition for the CMR systems (Ca, Ba or Pb doped), and in all cases the total edge shift from 0 to 300K is $`<`$ 0.04 eV. Although there is no obvious step or kink in the edge, expected for two well-defined valence states, there is a very small shape change that can be observed by taking the difference of data files at different temperatures. A dip/peak structure develops as T drops below Tc for the CMR samples; the dip/peak separation is $``$ 2 eV and is consistent with the splitting calculated for the px and py partial DOS when the manganite structure changes from an undistorted to a distorted (LaMnO3) lattice. For CMR samples, such changes in the local distortions below Tc were deduced earlier from EXAFS data. At low T the CMR samples are very well ordered, but as T increases there is a rapid increase in the local distortions up to T=Tc; above Tc the change in disorder changes slowly. The rapid change just below Tc has been associated with the formation of polarons. These distortions, now observed in both the XANES and EXAFS data, indicate some change in the local charge distribution. However the small size of the effect in the XANES spectra needs to be understood. In part it can be attributed to the extended nature of the broad Mn 4p band which tends to make the 1s-4p edge transition an average over several Mn atoms. However a change in covalency - specifically a transfer of charge between Mn 3d and O 2p states - might also be associated with this structural change, but produce little change in the edge. Support for this possibility is obtained from the pre-edge results, summarized below.

For the CO sample we observe a similar behavior, but in this case the structure in the difference spectra are inverted relative to that for the CMR sample. This indicates that the local distortions increase in the CO state below TCO.

The pre-edge structure provides additional information about the 3d-bands in these materials. Two or three peaks are observed, labeled A1-A3. A2 at 300K is essentially independent of concentration while A1 increases slowly with x; A3 is only observed for high Ca concentrations. Following the work of Elfimov et al. we attribute these peaks to a hybridization of Mn 4p on the excited atom with an ungerade combination of 3d states on neighboring Mn atoms, i.e. they are not the result of splittings of atomic multiplets on the excited atom as is often assumed. Similar explanations for the pre-edge region have recently been proposed for several other transition metal $`K`$-edges. Consequently the splittings observed are essentially unaffected by the presence of the core hole and should be a good measure of the splittings of the eg bands which are influenced by the hybridization of the Mn 3d and O 2p states. This interpretation of the pre-edge does not depend on small distortions of the crystal and therefore also provides a simple explanation for the large pre-edge features observed in the more ordered CaMnO3 material.

In the calculations of Elfimovet al., the two lowest empty bands are the majority and minority spin eg bands; the minority spin t2g band overlaps the latter but is expected to be more weakly coupled. U and J must be reduced slightly to fit the experimental splitting (2 eV) of the A1 and A2 peaks; U=4eV and JH=0.7eV. This indicates an increase in the covalency. The additional small decrease in the A1-A2 splitting below Tc may suggest a further change in covalency or hybridization.

Thus the picture that emerges is that there is considerable hybridization of the energy states (Mn 4p and 3d, and O 2p), with some hole density in the O bands and possibly only small differences in the charge localized on Mn atoms which have different types of eg orbitals. The possibility of distinct types of orbitals can lead to orbital ordering, with displacements of the O atoms forming J-T-like Mn-O bond distortions when the hopping charge is localized for times of order the optical phonon periods. As a result, the possibility that part of the transport takes place via hole density in the O bands needs to be considered. Note that slowly hopping holes on the O sites would lead to distorted Mn-O bonds while rapid hopping (faster than phonons) would leave the O atom at an average undistorted position.

###### Acknowledgements.

The authors wish to thank G. Brown, C. Brouder, D. Dessau, T. Geballe, J. Rehr, G. Sawatzky, and T. Tyson for useful discussions and comments. FB thanks K. Terakura for sending some of their unpublished results. The experiments were performed at the Stanford Synchrotron Radiation Laboratory, which is operated by the U.S. Department of Energy, Division of Chemical Sciences, and by the NIH, Biomedical Resource Technology Program, Division of Research Resources. Some experiments were carried out on UC/National Laboratories PRT beam time. The work is supported in part by NSF grant DMR-97-05117.


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# 1 Introduction

## 1 Introduction

The internal target of the HERA–B experiment consists of eight ribbons positioned around the proton beam of the HERA storage ring at a distance of $`36rms`$ beam widths . Protons drifting away from the beam core interact with these targets and are expected to produce among other hadrons B–mesons. Since 1992 we studied those problems of basic importance for the experiment  namely the interaction rate achievable and its fluctuations, the target efficiency, the spatial distribution of the interaction vertices, and the interference with the beams as well as the background induced by the wire target at the place of other experiments running in parallel to HERA–B. It turns out that the design goal of a target efficiency $`50\%`$ and the interaction rate of $``$ 40 MHz can be achieved .

The HERA–B detector with its readout and different trigger levels relies on the close correlation between the time of the interaction and the bunch crossing signal of the proton beam. Therefore this correlation was studied in some detail. Besides the interactions due to the bunched protons an unexpected high background from bunch uncorrelated interactions was observed, which showed a strong asymmetry in the transverse plane. In this paper we summarize the observations, quantify them and discuss possible sources of this background.

## 2 Coasting Beam

A schematic view of the target is shown in fig.1. Protons in the halo or close to the beam core interact with the target wires which are positioned inside/outside (“inner” and “outer” wire) and up/down (“upper” and “lower” wire) with respect to the center of the storage ring and the beam respectively. A sketch of the bunch structure of the HERA proton beam is shown in fig.2. The bunches are organized in $`36`$ trains, each consisting of 10 bunches of $`1ns`$ length. The bunch spacing within a train corresponds to $`96ns`$. The trains are separated by an empty bunch. 6 trains correspond to one fill of the PETRA preaccelerator, they are separated from the consecutive 6 trains by a gap of $`480ns`$. The last 15 buckets are empty to enable a safe beam dump (kicker gap). A complete revolution of a fill corresponds to $`22096ns=21.12\mu s`$.

A FADC system is used to record separately the contribution of each single bunch to the interactions produced at the target measured with scintillator hodoscopes . The FADC samples with the fourfold rate of the bunch crossing, i.e. every $`24ns`$ a signal is recorded. Per readout cycle of the FADC–system 880 bytes are recorded allowing to study the interactions in a time slice of 21.12 $`\mu s`$ which corresponds to the time needed by a proton to cycle once around the HERA ring. A rate of 150 Hz for the readout is achieved. About 5000 succeeding measurements are summed up to accomplish a reasonable statistics, hence the FADC rates presented in this paper are averaged over a time of $`30s`$. As demonstrated by fig.3a the target–beam halo interaction indeed shows the bunch structure of the proton beam if the protons interact with an inner target wire. The time structure of the outer target wires (fig.3b,c) differs qualitatively from the inner one, though the data were collected consecutively within a short time interval. While the inner wire provides a clear bunched signal, for the outer wire in addition to the bunch correlated events a continuous background is observed (fig.3b). Even in the regions of the empty RF–buckets and of the kicker gap a strong signal shows up if the outer wire is positioned in the beam halo. If the outer–target is hit by protons at a distance of $`5\sigma `$ from the beam center only the $`dc`$ component of the beam contributes (fig.3c). We have convinced ourselves that the observed interactions from the continuous component have the same signature as the bunch correlated events: exploiting the HERA–B Si–vertex detector it can be shown that the bunched and the $`dc`$ component of the proton beam interact with the wire, moreover the relative rates of different detector components for the two types of events are equal.

The difference of the time distributions for protons interacting with the inner and outer wire respectively hint to a $`dc`$ component of the machine current with an energy smaller than the synchronous protons $`\left(\mathrm{\Delta }E/E<0\right)`$ since at the position of the target the horizontal dispersion $`D_x`$ of the HERA proton–ring is negative and therefore the offset $`\mathrm{}x`$ of the beam due to its energy deviation $`\frac{\mathrm{\Delta }E}{E}`$ is positive, $`\mathrm{}x=D_x\frac{\mathrm{\Delta }E}{E}>0`$. The ratio of the integrated continuous background to the total interaction rate is smallest for the inner wire, followed by the lower and upper wire and it is largest for the outer wire (fig.4).

These observations can be explained easiest by discussing the particle trajectories in longitudinal phase space (fig.5) 111The HERA proton ring is operated with cavities excited at two different RF frequencies (52 MHz and 208 MHz). The figure is a simplified sketch for the case of a single frequency., where $`\mathrm{\Psi }`$ describes the longitudinal phase of a particle in a bunch and $`\dot{\mathrm{\Psi }}\frac{\delta p}{p}`$ the longitudinal momentum deviation of a particle with respect to the centroid. The boundary (separatrix) between the region of stable and unstable motion is characterized by the invariant

$$I\left(\frac{\delta p}{p}\right)^2\left(\frac{2Q_s}{h\alpha _p}\mathrm{cos}\frac{\mathrm{\Psi }}{2}\right)^2=0$$

| where | $`Q_s`$ | synchrotron tune |
| --- | --- | --- |
|  | $`h`$ | harmonic number |
|  | $`\alpha _p`$ | = $`\frac{\delta L/L}{\delta p/p}`$ momentum compaction factor |
|  | $`L`$ | path length of proton for 1 turn |

Particles in the stable region $`\left(I<0\right)`$ stay bunched while particles outside the stable region $`\left(I>0\right)`$ are debunched. These unbunched protons in case of the HERA storage ring deviate, depending on the voltage of the RF–system, by $`\frac{\mathrm{\Delta }E}{E}>\left(2\mathrm{}3\right)10^4`$ from the centroid particle. Note that the dynamic energy acceptance of the machine $`\frac{\mathrm{\Delta }E}{E}10^3`$ is much larger than $`\left(\frac{\mathrm{\Delta }E}{E}\right)_S=\left(2\mathrm{}3\right)10^4`$, the energy deviation of typical protons close to the separatrix. The results shown in figs.3, 4 demonstrate the evidence of an unbunched beam component with $`\mathrm{\Delta }E<0`$, the so called coasting beam.

Since these protons have smaller energies than the bunched particles an energy loss mechanism has to exist which forces the bunched protons to pass the separatrix and debunch. Besides machine inherent sources as synchrotron radiation ($`10eV`$ per turn), noise of the RF–system and intrabeam scattering the energy loss of protons in the target can produce the coasting beam. As far as these losses can be quantified they are much smaller than the maximum energy deviation of $`\mathrm{\Delta }E=0.27GeV`$ allowed for the stable longitudinal phase space at standard RF–voltage. Hence these energy losses are expected only to force protons near the separatrix to pass the phase space boundary of stable bunched beams.

### 2.1 Source of coasting beam

The first study was performed with a virgin beam, no electrons were stored in the electron–ring of the HERA storage–ring complex and the measurement started a few minutes after stable beam conditions were declared. In fig.6 b,c the position of the “outer” target with respect to the beam center of gravity is shown, the measured total interaction rate is plotted in fig.6a. At different times, indicated by the arrows on the time axis, FADC spectra were analyzed which allow to separate the bunch contribution from the coasting beam. In fig.7 the FADC spectra are plotted for the different time intervals. The data shown in fig.7a were collected when the target wire touched the beam for the first time. In this case the continuous coasting beam contribution to the interactions dominates. Since before this measurement no target wire had touched the beam this measurement unquestionably proves that the machine itself produces a coasting beam. Approaching further the beam core the bunch contribution starts to develop.

In the next step the target was withdrawn from the beam core and placed at a fixed position (fig.6 b,c). As shown by fig.6a the total interaction rate is strongly reduced but after a short time starts to increase again. Figs.7d,e demonstrate that the coasting beam “diffuses” faster towards the outer target than the bunched component, since no bunch correlated contribution is detected.

Further evidence for a machine induced coasting beam component follows from a second measurement. The total interaction rate and the position of the wires (inner I and outer II) at different times are shown in fig.8. At 19:15 the outer wire is moved towards the beam. An increase of the interaction rate and its fluctuations is observed. At 19:30 the outer wire is retracted, the interaction rate decreases strongly and recovers within the next half hour to a level of several MHz. This behaviour was already observed in fig.6. Starting at 20:18 the inner wire is moved towards the beam (fig.8c). As expected, the interaction rate increases. At 20:35 the inner wire is retracted by $`2mm`$ from the beam core, the interaction rate is strongly decreasing to the level observed for $`t<`$ 20:18. This behaviour is reproducible as shown by the measurements performed in the time interval 20:42 $`t`$ 21:12.

These results demonstrate that the energy loss of bunched particles due to interaction of the protons with the (inner) target wire is not a major source for producing the coasting beam. Comparing the interaction rate measured at $`t`$ = 20:18 and $`t`$ = 20:48 $`h`$, it follows that $`15\%`$ of the coasting beam interacting with the outer target was produced by energy loss of bunched protons in the inner target.

A similar conclusion can be drawn from fig.9. In this case the coasting beam component is detected (fig.9c) by a $`dc`$ current monitor. This current in good approximation stays constant for 15:00 $`t`$ 19:00, when the inner target was positioned at $`5.4\sigma `$ to $`3.9\sigma `$ from the beam core (fig.9b) and produced a high interaction rate of $`>`$ 30 MHz (fig.9a). Note, however, that in other measurements a slight increase of the current is observed for the same setup of the wire target. As demonstrated by fig.9c for $`t`$ 19:00 an increase of the $`dc`$ current is detected though the wire is pulled away from the beam (fig9b). Considering these effects one arrives again at a target contribution to the coasting beam of $`<`$ 20 %. Moreover, these observations stress the sensitivity of the observations on details of the machine setup, collimator positions etc.

Further details concerning the properties of the coasting beam follow from the measurement performed during machine studies where HERA was filled with 10 proton bunches. The contribution of these protons interacting with the target is shown in fig.10 in the time interval corresponding to channels 60 to 100. The coasting beam was excited by a kicker magnet in a narrow time slice around channel 460 every $`21.12\mu s`$, i.e. once per full turn of a fill. The measured distribution of the interaction rate (fig.10) shows an exponential increase of the rate which starts at channel $`300`$, peaks at channel $`460`$ and is followed by a sharp decrease.

The slope of the exponential corresponds to a characteristic “lifetime” of the protons of $`0.5\mu s`$ which can be explained as follows. The fraction of the coasting beam excited by the kicker produces a continuous beam of protons with large transverse emittance traveling around the storage ring with a slightly shorter circulation time than the synchronous protons since for coasting beam protons $`\alpha _p>0`$. Due to interactions of the protons with the target, the intensity of the excited beam component decreases with time.

A proton interacts in the target after typically $`10^5`$ revolutions . From fig.10 one concludes that at this time it has advanced by $`0.5\mu s`$ with respect to the synchronous protons if it belongs to the coasting beam. Therefore after $`n=21.12\mu s/0.5\mu s10^5`$ turns corresponding to a typical scale of $`t=21.12\mu sn90s`$, the non–interacting excited protons in the coasting beam are smeared homogenously around the ring. This time has to be compared to the time needed by a proton close to the separatrix to advance by a full turn with respect to a centroid proton. The order of magnitude is given by

$$t=\frac{L}{\mathrm{\Delta }L}21.12\mu s=\frac{1}{\alpha _p\frac{\mathrm{\Delta }E}{E}}21.12\mu s80s$$

where $`\frac{\mathrm{\Delta }L}{L}`$ is the relative deviation of the path length for coasting protons, $`\alpha _p=1.310^3`$ is the momentum compaction factor of HERA and $`\left(\frac{\mathrm{\Delta }E}{E}\right)_S(2\mathrm{}3)10^4`$ the energy deviation of typical protons close to the separatrix. Given the fact that the estimates are quite rough, the two time scales are in remarkable agreement.

### 2.2 Impact of coasting beam on target operation

Measurements performed with an old fill are shown in figs.1112. Until t=14:12 the inner target was operated with a constant interaction rate of $``$ 10 MHz. The continuous background due to coasting beams is negligible (fig.12a), and the contribution of bunch correlated interaction dominates. At the time 14:12, the inner target was retracted and the outer target was inserted (fig.11b). The results shown in fig.12b–d demonstrate that now nearly 100 % of the interaction rate measured under these conditions is due to coasting beam protons. Initially, strong fluctuations of the interaction rate are observed while the wire is gradually scraping away the halo and moving towards the beam core (fig.11a). At $`t`$ = 15:00 the fluctuations disappear abruptly and the wire stops moving towards the beam. At the same time, the coasting beam background drops by a factor of two, as can be seen from data taken at the times 14:59 (fig.12d) and 15:03 (fig.12e). With further operation of the outer target wire at constant interaction rate, the coasting beam background thereafter continues to decrease slowly (fig.12f). These effects can be interpreted by the transition of the wire moving from the pure coasting beam halo into the beam core region. In this sense the outer wire acts effectively like a scraper for the coasting beam halo.

Similar to the measurements described in section 2.1 a steady increase of the rate with time (fig.11b) is observed, indicating the repopulation of the halo, if the outer wire is retracted by $`0.5mm`$ (fig.11a). The time structure of the proton bunches disappeares completely and the interactions are again caused by the remaining coasting beam component at large betatron amplitudes.

Note that the time dependence for the two rate measurements presented above are similar and reproducible. They are indicative of the inherent beam dynamics, leading to beam diffusion describable by the Fokker–Planck equation . The sudden drop of the coasting beam contribution observed at $`t=`$ 15:00 in the measurement discussed above deserves special attention and will be further analyzed by time resolved measurements which are presently being prepared.

## 3 Conclusions

We have detected a continuous current of protons in the HERA machine which produces nonbunched background at the HERA–B target. Since the experiment is positioned at a location with a negative dispersion, this observation can be attributed to protons with a smaller energy than the synchronous ones. The measurement of the circulation time difference of protons for the coasting beam and synchronous protons and its quantitative agreement with estimates from linear beam optics support this interpretation. We have shown that the coasting beams exist already for a virgin fill of the proton ring which is not disturbed in advance by proton interactions with the target. The interactions of bunched protons with the target increases the intensity of the coasting beam only marginally.

Moreover the protons of the coasting beam diffuse faster into the halo region than the bunch correlated protons. A surprising observation is the simultaneous sudden decrease of the rate fluctuations and the coasting beam contribution at a characteristic wire–beam distance, indicating a transition from the pure coasting beam halo into the (mainly bunched) beam core. With an improved setup we plan to study the effects with higher time resolution.

### Acknowledgement

This work was supported by the BMBF Bonn under contract number 05 7Do55P and 057Bu35I. The observations presented in this paper and their understanding has been obtained in close and fruitful collaboration with the HERA machine physicists. All further progress to understand and overcome the problems related with coasting beam at HERA requires still a close cooperation and the support of the HERA machine group.

We like to express our cordial thanks to the HERA crew for the friendly collaboration, their support and their assistance to discuss our observations and to carry out dedicated machine studies to investigate and improve the situation.

It is impossible to name all of them, special thanks we owe to Jim Ellis, B. Holzer, Jens Kluthe, Helmut Mais, Chr. Montag, Mark Lomperski, Tanaji Sen, F. Willeke and Mari Paz Zorzano.


text:
# Antiferromagnetic Correlations versus Superfluid Density in La2-xSrxCuO4

## Abstract

We have performed muon spin relaxation and low field $`ac`$-susceptibility measurements in a series of high quality samples of La2-xSrxCuO4 ($`x=0.080.24`$) as a function of temperature. Superconductivity is found to coexist with low temperature spin glass order up to the optimally doped region where the normal state pseudogap also closes. The systematic depletion of the superfluid density with the enhancement of aniferromagnetic correlations with underdoping indicates a $`competition`$ between antiferromagnetic correlations and superconductivity.

Establishing and understanding the phase diagram of the high-$`T_c`$ superconductors (HTS) versus temperature and doping has been one of the major challenges in modern solid state physics. The parent compound La2CuO4 of the first HTS family to be discovered, La2-xSrxCuO4, is an insulator exhibiting long range antiferromagnetic (AF) order, which is eventually destroyed as carriers are doped into the CuO2 planes. After passing through a spin glass (SG) state superconductivity emerges near 0.06 holes/planar-Cu-atom and follows an approximately parabolic doping dependence until it disappears at $`x`$0.30. Spectroscopic evidence however, indicates that AF correlations do not seize to exist with the emergence of superconductivity, but instead a short range ordered AF state persists in the superconducting state . This observation raises fundamental questions as to how far into the superconducting regime of the phase diagram these AF correlations persist and how, if at all, these affect the superconductivity.

In this short paper we present briefly new experimental findings in which the signatures of antiferromagnetic correlations is observed to persist up to $`x`$0.17. We find a close correlation between the doping dependence of the AF and the absolute value of the superfluid density, $`\rho ^s(0)`$. The latter is almost constant for approximately $`x>0.17`$ and drops with the enhancement of the AF fluctuations, undergoing an increased depletion in the vicinity of the stripe phase region ($`x=0.125`$). These results suggest that the AF order parameter competes with the superconducting counterpart in more than $`50\%`$ of the superconducting region of the phase diagram.

The samples studied were single-phase polycrystalline La2-xSrxCuO4 (LSCO) ($`x=`$ 0.08, 0.10, 0.125, 0.15, 0.17, 0.20, 0.22, 0.24) prepared using solid-state reaction procedures. No other phases were detected by powder x-ray diffraction and the phase purity is thought to be better than $`1\%`$. High field magnetic susceptibility measurements showed no signatures of excess paramagnetic centres and the measured values of $`T_c`$ and lattice parameters are also in very good agreement with published work . The samples have been extensively characterised by several transport, magnetic and spectroscopic techniques, all indicating their high quality. Zero-field (ZF) and transverse-field (TF) $`\mu `$SR experiments were performed at the pulsed muon source, ISIS Facility, Rutherford Appleton Laboratory. The samples were mounted on a silver plate either on the cold stage of a dilution refrigerator or in a variable temperature helium cryostat, enabling spectra to be collected over the temperature range $`40mK`$ to $`50K`$. The in-plane magnetic penetration depth, $`\lambda _{ab}`$, ($`\lambda _{ab}^2`$ $``$ $`\rho ^s`$) was determined both by a low-field $`ac`$-susceptibility technique (typically at $`1G`$ and $`333Hz`$) on grain-aligned powders and from the analysis of TF-cooled $`\mu `$SR measurements. The latter were carried out on unaligned powders in a field of $`400G`$. Details for deriving $`\lambda _{ab}`$ in HTS from the measured low-field $`ac`$-susceptibility and TF-$`\mu `$SR spectra can be found elsewhere .

In Fig.1 we present the time evolution of the ZF muon asymmetry for $`x=0.08`$ ($`T_c=21K`$) as a function of temperature. In all samples the high temperature form of the depolarisation is Gaussian, consistent with dipolar interactions between the muons and their near neighbour nuclear moments. This was verified by applying a $`50G`$ longitudinal field, which completely suppressed the depolarisation. As the temperature is lowered the onset of dynamical relaxation processes becomes apparent in the change in the shape of the depolarisation function. The samples with $`x=0.08,0.10`$ and $`0.125`$ follow the same pattern, which is indicative of the onset of spin glass ordering at low temperature. For simplicity, we have chosen to parametrise the form of the depolarisation function as a stretched exponential, $`G_z(t)`$ = $`A_1`$ $`exp[(\lambda t)^\beta ]`$ \+ $`A_2`$. The constant term $`A_2`$ accounts for a small time independent background arising from muons stopping in the silver backing plate. At high temperatures we find that the value of $`\beta `$ $``$ 2, but for samples with $`x<0.15`$ it decreases smoothly to a value approaching $`0.5`$ at low temperatures. This ”root exponential” behaviour is widely found in the temperature regime just above the glass temperature in spin glasses . The temperature dependence of $`\beta `$ for the present samples is shown in Fig. 2. We have used the temperature at which the value of $`\beta `$ drops below 2 as the onset temperature for AF correlations $`T_{sf}`$, and the temperature where $`\beta `$ $``$ 0.5 as a measure of $`T_{sg}`$ the spin glass freezing temperature. We find that for the $`x<0.08`$ sample for example, the relaxation rate parameter $`\lambda ^\beta `$ is peaked close to $`T_{sg}`$ (Fig. 3). At temperatures below $`T_{sg}`$ the form of the depolarisation function changes: there is an initial rapid decay of $`G_z(t)`$, followed by a slowly damped tail (see left hand panel in Fig. 1). This behaviour is very characteristic of the behaviour of spin glasses below $`T_{sg}`$, and has been attributed by Uemura $`et`$ $`al`$,  to the effects of the static distribution of field, combined with dynamical processes in the frozen spin glass state.

The present data show that SG freezing persists up to and beyond $`x=0.125`$. Indeed the onset of AF correlations for $`x=0.125`$ occurs at a higher temperatures than for $`x=0.10`$. This is probably associated with the formation of stripe domains in this range of concentration . For $`x=0.15`$ and $`0.17`$ the trends of $`\beta (T)`$ suggest a very small value of spin glass temperature $`T_{sg}`$ ($`<45mK`$) with fluctuations setting just below 8K and 2K, respectively. This suggests that for higher dopings the AF correlations are absent or at least beyond experimental range.

In Fig. 4 we summarise the essence of this work by comparing the doping dependence of $`T_{sf}`$ and $`T_{sg}`$, (including data for $`T_{sg}`$ from ref. ), with that of $`\lambda _{ab}(0)^2`$ $``$ $`\rho ^s(0)`$. We note that our vales of $`T_{sg}`$ for $`x=0.08`$ and $`0.10`$ are in excellent agreement with those reported in ref. . Figure 4 indicates that although the freezing of spins occurs at very low temperatures, $`T_{sg}`$ $``$ $`T_c`$, magnetic fluctuations are apparent at significantly higher temperatures ($`e.g.`$, $`T_{sf}0.5T_c`$ for $`x=0.10`$ and $`T_{sf}0.2T_c`$ for $`x=0.15`$). Therefore, a large fraction of the supeconducting region of the phase diagram coexists with AF picking up near $`x=1/8`$ and eventually disappearing in the lightly overdoped region where the normal state (or pseudo) gap, $`\mathrm{\Delta }_N`$, is known to close , suggesting a connection between $`\mathrm{\Delta }_N`$ and antiferromagnetic correlations.

As shown in Fig. 4, the superfluid density is doping independent in the region where $`T_{sg}`$ = $`T_{sf}`$ $`=0`$ and is gradually reduced with the increased evolution of AF correlations ($`ie`$., for $`x<0.20`$), undergoing a local dip in the $`1/8`$ region where AF is enhanced possibly due to the stripe phase. We would like to note the striking parallel changes in $`\rho ^s(0)`$ with $`T_{sg}`$, $`T_{sf}`$ emphasising the intimate connection of $`\rho ^s(0)`$ with the AF background rather than simply $`T_c`$.

The present results suggest that AF coexists with superconductivity in the underdoped and slightly overdoped samples and becomes undetectable in the heavily overdoped regime where the pseudogap also disappears. The systematic depletion of the superfluid density with increasing AF correlations (Fig. 4) indicates that the latter $`compete`$ with superconductivity and $`\rho ^s(0)`$ is not simply a function of $`T_c`$

We are grateful to Dr A.D. Taylor of the ISIS Facility, Rutherford Appleton Laboratory for the allocation of muon beam time. C.P. thanks Tao Xiang for useful discussions and Trinity College, Cambridge for financial support.

FIGURE CAPTIONS

Figure 1. Typical zero-field $`\mu `$SR spectra of La2-xSrxCuO4 for $`x=0.08`$ measured at $`1.3,5`$ and $`9K`$. The solid lines are fits of the stretched exponential, $`G_z(t)`$ = $`A_1`$ $`exp[(\lambda t)^\beta ]`$ \+ $`A_2`$ (see text for details).

Figure 2. Temperature dependence of the exponent $`\beta `$ of La2-xSrxCuO4 for $`x=0.08,0.10,0.125,0.15,0.17`$.

Figure. 3. Temperature dependence of the relaxation rate parameter $`\lambda ^\beta `$ of La2-xSrxCuO4 for $`x=0.08,0.10,0.125,0.15,0.17`$.

Figure 4. Phase diagram of La2-xSrxCuO4 showing the doping dependence of $`T_c`$ (closed lower triangles), $`T_{sg}`$ (closed circles), $`T_{sf}`$ (closed squares), and $`\lambda _{ab}(0)^2`$ $``$ $`\rho ^s(0)`$ (closed upper triangles). Open cirlces are data for $`T_{sg}`$ taken from ref. . A schematic variation of the Nell temperature $`T_N`$ is also shown as a broken line.


text:
# Confinement and the AdS/CFT Correspondence

## I Introduction

It was realized many years ago  that in the large N limit of Yang-Mills theory a remarkable simplification takes place: the physics is dominated by “planar” graphs, Feynman diagrams with no line-crossings. In this limit, the gauge theory ought to be described by a “QCD string,” and it was a hope that such a simplification might shed light on some of the mysteries of nonabelian gauge theories, notably the puzzle of confinement.

The AdS/CFT correspondence  makes explicit this relation between gauge fields and strings. Specifically, the correspondence says that IIB string theory in a background of five-dimensional anti-de Sitter space times a five-sphere is dual to the large N limit of $`𝒩=4`$ supersymmetric Yang-Mills theory in four dimensions. This is a conformal theory with no confinement; however, the thermal theory in finite volume could still have a confined phase.

An important ingredient in the correspondence is the principle of holography , the notion that the physics of a gravitational theory is dual to a different theory in one lower dimension. Conversely, given the dual theory on a boundary, we must consider all the possible bulk manifolds whose boundaries have the same intrinsic geometry as the background of the dual theory . For thermal super Yang-Mills on $`S^3`$, there are at least two distinct Einstein manifolds with the requisite boundary geometry: thermal anti-de Sitter space and a Schwarzschild-like black hole in AdS . These classical bulk solutions are a sort of master field of the gauge theory. The distinct geometries are interpreted in the gauge theory as different phases in the strong ’t Hooft coupling limit; the thermodynamics of the black hole corresponds to the thermodynamics of strong-coupling SYM in the unconfined phase while thermal AdS is seen as dual to the confined phase of the gauge theory.

In this paper, we investigate the thermodynamics of the different phases of super Yang-Mills at finite volume on $`S^3`$ using the AdS/CFT correspondence. In particular, we examine the conditions for phase change in a microcanonical framework. Formally, a phase transition cannot occur in finite volume at finite N. However, a crossover between these qualitatively different phases can still occur when their weights in the partition sum are the same. In the dual picture, the black hole dominates the path integral when the horizon is large compared to the inverse AdS curvature, and the thermal AdS geometry dominates for sufficiently low temperatures. The crossover between these two geometries is known as the Hawking-Page transition and corresponds in the field theory to a transition between the confining and unconfined phases. Since a microcanonical framework requires that energy be conserved during any transition, we shall consider not empty AdS with thermal identifications, but rather thermally-identified AdS with a thermal gas in it. The energy of the system is then measured with respect to the thermal AdS background.

This paper is structured as follows. We begin, in Section II, by reviewing the thermal properties of AdS black holes and their interpretation in light of the AdS/CFT correspondence. Then, in Section III, we consider a thermal bath in AdS. Finally, in Section IV, we determine the necessary conditions for a crossover between the black hole and radiation-dominated phases.

## II AdS Black Holes

The five-dimensional Einstein-Hilbert action with a cosmological constant is given by

$$I_{\mathrm{BH}}=\frac{1}{16\pi G_5}d^5x\sqrt{g}\left(R+12l^2\right),$$
(1)
where $`G_5`$ is the five-dimensional Newton constant, $`R`$ is the Ricci scalar, the cosmological constant is $`\mathrm{\Lambda }=6l^2`$, and we have neglected a surface term at infinity. Anti-de Sitter solutions derived from this action can be embedded in ten-dimensional IIB supergravity such that the supergravity background is of the form $`AdS_5\times S^5`$.

The line element of a “Schwarzschild” black hole in anti-de Sitter space  in five spacetime dimensions can be written as

$$ds^2=\left(1\frac{2MG_5}{r^2}+r^2l^2\right)dt^2+\left(1\frac{2MG_5}{r^2}+r^2l^2\right)^1dr^2+r^2d\mathrm{\Omega }_3^2,$$
(2)
where $`l`$ is the inverse radius of AdS space. This solution has a horizon at $`r=r_+`$ where

$$r_+^2=\frac{1}{2l^2}\left(1+\sqrt{1+8MG_5l^2}\right).$$
(3)
When $`r_+l1`$, the black hole could become unstable to localization on the $`S^5`$ by an analog of the Gregory-Laflamme mechanism . As a rule, one may determine a necessary (though not sufficient) condition for instability from entropic considerations. A straightforward computation then shows that localization instability could occur for very small black holes with $`r_+l1`$ . Here we shall work with black holes with $`r_+l>1`$ for which we do not expect such an instability.

To study the black hole’s thermodynamics, we Euclideanize the metric. The substitution $`\tau =it`$ makes the metric positive definite and, by the usual removal of the conical singularity at $`r_+`$, yields a periodicity in $`\tau `$ of

$$\beta _{\mathrm{BH}}=\frac{2\pi r_+}{1+2r_+^2l^2},$$
(4)
which is identified with the inverse temperature of the black hole. The entropy is given by

$$S_{\mathrm{BH}}=\frac{A}{4G_5}=\frac{\pi ^2r_+^3}{2G_5},$$
(5)
where $`A`$ is the “area” (that is, three-volume) of the horizon. The mass above the anti-de Sitter background is

$$U_{\mathrm{BH}}=\frac{3\pi }{4}M=\frac{3\pi }{8G_5}r_+^2\left(1+r_+^2l^2\right).$$
(6)
This is the AdS equivalent of the ADM mass, or energy at infinity. (Actually if the black hole is to be considered at thermal equilibrium it should properly be regarded as being surrounded by a thermal envelope of Hawking particles. Because of the infinite blueshift at the horizon, the envelope contributes a formally infinite energy. Here we shall neglect this infinite energy as unphysical, absorbed perhaps by a renormalization of the Newton constant.) We can now also write down the free energy:

$$F_{\mathrm{BH}}=\frac{\pi r_+^2}{8G_5}\left(1r_+^2l^2\right).$$
(7)
Eqs. (5-7) then satisfy the first law of thermodynamics. To express them in terms of the gauge theory parameters $`N`$, $`T_{\mathrm{CFT}}`$, and $`V_{\mathrm{CFT}}`$, we substitute physical data taken from the boundary of the black hole spacetime. At fixed $`rr_0r_+`$, the boundary line element tends to

$$ds^2r_0^2\left[l^2dt^2+d\mathrm{\Omega }_3^2\right],$$
(8)
giving a volume of

$$V_{\mathrm{CFT}}=2\pi ^2r_0^3.$$
(9)
The field theory temperature is the physical temperature at the boundary:

$$T_{\mathrm{CFT}}=\frac{T_{\mathrm{BH}}}{\sqrt{g_{tt}}}\frac{T_{\mathrm{BH}}}{lr_0}.$$
(10)
To obtain an expression for $`N`$, we invoke the AdS/CFT correspondence. This relates $`N`$ to the radius of $`S^5`$ and the cosmological constant:

$$R_{S^5}^2=\sqrt{4\pi g_s\alpha _{}^{}{}_{}{}^{2}N}=\frac{1}{l^2}.$$
(11)
Then, since

$$(2\pi )^7g_s^2\alpha _{}^{}{}_{}{}^{4}=16\pi G_{10}=16\frac{\pi ^4}{l^5}G_5,$$
(12)
we have

$$N^2=\frac{\pi }{2l^3G_5}.$$
(13)
With these substitutions, we see that in the limit $`r_+l1`$, the black hole entropy can be expressed in terms of conformal field theory parameters as

$$S_{\mathrm{BH}}=\frac{2}{3}\pi ^2N^2V_{\mathrm{CFT}}T_{\mathrm{CFT}}^3.$$
(14)
The dimensionful terms in this expression are in accord with expectations for a conformal theory. The matching has been extended  to rotating black holes and their field theory dual, Yang-Mills with angular momentum. The dependence on $`N^2`$ indicates that the conformal field theory is in its unconfined phase; the $`N^2`$ species of free gluons make independent contributions to the free energy. We shall see in the next section that the thermodynamics of the confined phase is rather different.

## III A hot bath in AdS

Now consider a gas of thermal radiation in anti-de Sitter space. The energy eigenstates of $`AdS_5`$ are :

$$\mathrm{\Psi }_{\omega jmn}(r,t,\theta ,\varphi ,\psi )=N_{\omega j}\mathrm{exp}\left(i\omega lt\right)\mathrm{sin}^j\rho C_{\omega j1}^{j+1}(\mathrm{cos}\rho )Y_j^{mn}(\theta ,\varphi ,\psi ),$$
(15)
with the condition $`\omega 1j|m|,|n|`$ where $`C_q^p(x)`$ are Gegenbauer polynomials, $`Y_j^{mn}(\theta ,\varphi ,\psi )`$ are the spherical harmonics in five-dimensional spacetime (with total angular momentum number $`j`$), and $`\rho \mathrm{arctan}(rl)`$. Here $`\omega `$ is an integer and hence the spectrum is quantized in units of $`l`$, the inverse “radius” of AdS. Since this is also the quantum of excitations of the five-sphere, we should consider thermodynamics over the full ten-dimensional space. The appropriate line element is therefore

$$ds^2=\left(1+r^2l^2\right)dt^2+\left(1+r^2l^2\right)^1dr^2+r^2d\mathrm{\Omega }_3^2+l^2d\mathrm{\Omega }_5^2.$$
(16)
To obtain a thermal field theory, we again Euclideanize the metric. The periodicity of $`\tau =it`$ is then the inverse (asymptotic) temperature, $`T_{\mathrm{AdS}}^1`$, of the theory; the absence of a horizon means that $`T_{\mathrm{AdS}}`$ is an arbitrary parameter. However, the relevant temperature for thermodynamics in the bulk is not $`T_{\mathrm{AdS}}`$, but the local, redshifted, temperature:

$$T_{\mathrm{local}}=\frac{T_{\mathrm{AdS}}}{\sqrt{g_{tt}}}=\frac{T_{\mathrm{AdS}}}{\sqrt{1+r^2l^2}}.$$
(17)
To calculate thermodynamic quantities we foliate spacetime into (timelike) slices of constant local temperature. Extensive thermodynamic quantities are then computed by adding the contribution of each such hypersurface.

The local five-dimensional energy density of the thermal gas of radiation can be written as

$$\rho _{\mathrm{local}}=\sigma \frac{\pi ^3}{l^5}T_{\mathrm{local}}^{10},$$
(18)
where we have neglected infrared effects due to curvature or nonconformality. Here $`\sigma `$ is the ten-dimensional supersymmetric generalization of the Stefan-Boltzmann constant, which is approximated by its flat space value:

$$\sigma =\frac{62}{105}\pi ^5,$$
(19)
where we have included a factor of 128, the number of massless bosonic physical degrees of freedom of IIB supergravity.

The total “ADM” energy-at-infinity of a gas contained in a ball of radius $`r_0`$ is then

$$U_{\mathrm{gas}}^{\mathrm{}}=\sigma \frac{\pi ^3}{l^4}T_{\mathrm{local}}^{10}\sqrt{g_{tt}}\sqrt{g_{rr}}r^3𝑑r𝑑\mathrm{\Omega }_3=\frac{2\pi ^5}{l^5}\sigma T_{\mathrm{AdS}}^{10}_0^{r_0}\frac{r^3dr}{(1+r^2l^2)^5}\sigma V_{\mathrm{eff}}(r_0)T_{\mathrm{AdS}}^{10}.$$
(20)
Here the additional blueshift factor of $`\sqrt{g_{tt}}`$ converts the local (fiducial) energy into an ADM-type energy, comparable to Eq. (6). We have also defined an effective volume,

$$V_{\mathrm{eff}}(r_0)=\frac{2\pi ^5}{l^9}\left(\frac{2}{3}\frac{2+3(r_0l)^2}{3\left(1+(r_0l)^2\right)^{3/2}}\right),$$
(21)
which, as $`r_0\mathrm{}`$, approaches

$$\frac{4\pi ^5}{3l^9}.$$
(22)
Thermodynamically, anti-de Sitter space behaves as if it had a finite volume.

Similarly, the other thermodynamic quantities of the thermal bath are

$$F=\frac{\sigma }{9}V_{\mathrm{eff}}T_{\mathrm{AdS}}^{10},S=\frac{10}{9}\sigma V_{\mathrm{eff}}T_{\mathrm{AdS}}^9,$$
(23)
consistent with the first law of thermodynamics. The absence of a $`G_5`$ in the free energy indicates, from the CFT point of view, that the free energy is of order $`N^0`$. This is the confined phase of the theory – the free energy is of order $`N^0`$ because the $`N^2`$ species of gluons have condensed into hadronic color singlets. (Curiously, attempts to formulate confinement in terms of anti-de Sitter space date back at least to the 1970’s .)

The factor of nine spatial dimensions in the volume is somewhat puzzling for a three-dimensional gauge theory. It reflects the fact that the QCD (SYM) string is really a type IIB string which naturally lives in nine spatial dimensions. It has been suggested that the extra dimensions in which the open string worldsheet bounded by a Wilson loop can extend are akin to Liouville dimensions .

## IV The Crossover

A field theory living on a manifold, $`S^3\times S^1`$ with three-sphere radius $`r_0`$, is dual to those five-dimensional Einstein manifolds that have the same geometry at $`r_0`$. In the microcanonical approach that we shall follow, the contributions to the partition function come from both the black hole and the gas in thermally-identified AdS where the energy of the gas and black hole are taken to be the same:

$$Z(U)=e^{I_{\mathrm{BH}}(U)}+e^{I_{\mathrm{gas}}(U)}.$$
(24)
Which of these two thermodynamic phases the system is found in is determined, in the saddle point approximation, by the relative values of the respective Euclidean classical actions. The action of the black hole is simply the Einstein-Hilbert action, Eq. (1). This is proportional to the volume of the spacetime and so needs to be regulated. A finite action is obtained by subtracting the (also infinite) action for thermally-identified anti-de Sitter space in which the hypersurface at a constant large radius has the same intrinsic geometry as a hypersurface at the same radius in the black hole background . The regularized black hole action is

$$I_{\mathrm{BH}}=\frac{\pi ^2r_+^3}{4G_5}\frac{1r_+^2l^2}{1+2r_+^2l^2}.$$
(25)
Subtracting the anti-de Sitter background is equivalent to choosing the ground state of the theory. Then the comparable value of the action for the gas in thermally-identified AdS should be just the action of the gas itself, namely $`F/T`$. Thus

$$I_{\mathrm{gas}}=\frac{1}{9}\sigma V_{\mathrm{eff}}T_{\mathrm{AdS}}^9.$$
(26)
The qualitative thermodynamic behavior of the system is determined by the action which dominates the partition function Eq. (24). At the crossover between the two phases, the action for the gas and the black hole are the same. Moreover, energy must be conserved. Hence one may determine the conditions for a smooth crossover from the following equations:

$$U_{\mathrm{gas}}^{\mathrm{local}}=U_{\mathrm{BH}}^{\mathrm{local}},I_{\mathrm{gas}}=I_{\mathrm{BH}}.$$
(27)
Note that, since the two phases cannot be in physical contact, the physical temperature does not have to be the same for the two phases. (The physical temperatures are the same at $`r_+l=\sqrt{7}`$.)

Solving these equations yields $`N^2`$ as a function of the dimensionless quantity $`xr_+l`$ at the crossover:

$$N^2=\frac{31}{2^53^{13}57}\frac{(1+x^2)^9(1+2x^2)^{10}}{(x^21)^{10}x^{12}}.$$
(28)
How accurate is this equation? In using Eq. (17), we have omitted the back-reaction of the gas on the metric. One may estimate this. Consider a spherically symmetric stationary spacetime with a cosmological constant and massive matter fields. The equation of hydrostatic equilibrium (equally, the $`tt`$ Einstein equation) reads

$$\frac{d}{dr}m(r)=8\pi ^2r^3\left(G_5\rho +\mathrm{\Lambda }\right),$$
(29)
where $`g_{tt}1m(r)/r^2`$. Back-reaction can reliably be neglected when the matter term in the parenthesis is (much) smaller than the cosmological term. For an energy density given by Eq. (18) and a total energy matched to that of the black hole phase, Eq. (6), the condition $`G_5\rho <|\mathrm{\Lambda }|`$ amounts to

$$\frac{9\pi }{32}x^2(1+x^2)l^2<6l^2,$$
(30)
and we see that the matter term becomes dominant at large $`x`$, and is not entirely negligible even near $`x=1`$. At high temperature, therefore, Eq. (28) becomes unreliable; this limit has been studied elsewhere . To accommodate the effect of matter, one might try to seek a solution to the linearized Einstein equations, perturbed around the $`AdS_5`$ background. The exact form of Eq. (28) would also be modified by including the correct Stefan-Boltzmann constant for anti-de Sitter space. And finally, when $`N`$ is small, the supergravity approximation itself breaks down.

Despite these caveats, Eq. (28) seems to capture the correct qualitative behavior. In Fig. 1, we plot $`N`$ near the crossover for $`x1`$. The region below the crossover curve is dominated by the confined or AdS gas phase, whereas the region above is dominated by the unconfined or black hole phase. Note that $`x`$ grows roughly like the dimensionless product $`T_{\mathrm{phys}}r_0`$. As the temperature/volume increases, the graph confirms our expectation that the theory becomes conformal. As $`N`$ goes to infinity, we recover the result  that the transition occurs at $`r_+l=1`$. This is in fact a very good approximation for finite but large N.

Acknowledgments

We would like to thank José Barbón, Gerard ’t Hooft, Shiraz Minwalla, and Erik Verlinde for helpful discussions. D. B. is supported by European Commission TMR programme ERBFMRX-CT96-0045, and would like to acknowledge the hospitality of the Spinoza Institute, CERN and the support of ITF, Utrecht. M. P. is by the Netherlands Organization for Scientific Research (NWO).