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# Surf. Sci. (in press) Surface Core-Level Shifts at an oxygen-rich Ru Surface: O/Ru(0001) vs. RuO2(110)

## I Introduction

In addition to the long-standing interest in RuO2 as a technologically relevant metallic oxide per se, this material has recently also received a lot of attention as the end product in the oxidation sequence of ruthenium surfaces . Epitaxially well oriented, incommensurate RuO2(110) domains were identified on Ru(0001) after heavy oxygen exposure and related to the enhanced catalytic activity towards CO oxidation , observed at Ru under high oxygen partial pressure . Subsequently, an atomistic mechanism for this surface-oxide formation was proposed , in which after the completion of the full monolayer O$`(1\times 1)`$ chemisorption phase on the surface, O penetrates into the sample and clusters in islands between the first and second metallic layer, locally decoupling a O-Ru-O trilayer from the underlying substrate. The ongoing oxidation results in more and more of these trilayers, which finally unfold into the more open rutile structure giving rise to (110) oriented RuO2 patches on the surface.

Depending on the O partial pressure, a real Ru(0001) surface will therefore exhibit a rather complex morphology, ranging from chemisorbed O overlayers to sub-surface O and RuO2(110) patches with different surface terminations. Given this low degree of structural order, X-ray photoelectron spectroscopy (XPS) appears as a well suited tool to study the oxidation process in detail. However, the complex core-level spectra to be expected from such a surface with a manyfold of peaks due to coexisting domains will render the interpretation of the obtained data not unambiguous. This is even aggravated by the fact, that already for the RuO2(110) surface alone the origin of the peaks has been discussed controversially .

To provide a theoretical guidance for the experimental data analysis, we thus calculated all Ru $`3d`$ and O $`1s`$ surface core-level shifts (SCLSs) for the individual, already identified domains on an oxygen-rich Ru(0001) surface, namely the O$`(1\times 1)`$ chemisorbed phase, as well as two different surface terminations of RuO2(110). With this, we will show that certain peaks may be used as a fingerprint for the existence of one or the other domain.

## II Theoretical

The SCLSs are obtained from density-functional theory (DFT) calculations within the generalized gradient approximation (GGA) of the exchange-correlation functional . The full-potential linear augmented plane wave method (FP-LAPW)  is used to solve the Kohn-Sham equations. We model the O$`(1\times 1)`$/Ru(0001) surface with a six layer slab, adsorbing O on both sides to preserve mirror symmetry. Likewise, the RuO2(110) surface is represented by a symmetric slab consisting of 3 rutile O-(RuO)-O trilayers. A vacuum region of $``$11Å was employed to decouple the surfaces of consecutive slabs in the supercell approach. The resulting, fully relaxed geometries are in very good agreement with previous LEED and DFT studies .

The FP-LAPW basis set is taken as follows: $`R_{\mathrm{MT}}^{\mathrm{Ru}}=`$1.8 bohr, $`R_{\mathrm{MT}}^\mathrm{O}=`$1.3 bohr, wave function expansion inside the muffin tins up to $`l_{\mathrm{max}}^{\mathrm{wf}}=12`$, potential expansion up to $`l_{\mathrm{max}}^{\mathrm{pot}}=4`$. The Brillouin zone integration for the O$`(1\times 1)`$/Ru(0001) and RuO2(110) was performed using a $`(12\times 12\times 1)`$ and $`(5\times 10\times 1)`$ Monkhorst-Pack grid with 19 and 15 k-points in the irreducible part respectively. The energy cutoff for the plane wave representation in the interstitial region between the muffin tin spheres was 17 Ry for the wave functions and 169 Ry for the potential.

The SCLS, $`\mathrm{\Delta }_{\mathrm{SCLS}}`$, is defined as the difference in energy which is needed to remove a core electron either from a surface or from a bulk atom . We calculate this quantity both in the initial-state approximation, as well as taking final-state effects into account. In the prior approximation, the SCLS is simply due to the variation of the orbital eigenenergies before the excitation of the core electron. Yet, the total, measurable SCLS involves an additional component due to the screening contribution from the valence electrons in response to the created core hole. We obtain this total shift, $`\mathrm{\Delta }_{\mathrm{SCLS}}^{\mathrm{total}}`$, via the Slater-Janak transition state approach of evaluating total energy differences  using impurity type calculations where an ionized atom is once placed at the surface and once in the bulk. In order to decouple these ionized atoms from each other, we surround them with neighbours possessing the normal core configuration by performing the calculation in a $`(2\times 2)`$ and a $`(2\times 1)`$ supercell for Ru(0001) and RuO2(110) respectively. Having calculated both the total and the initial-state SCLS allows us then to single out the final-state effect from their respective difference. The procedure and numerical accuracy of both types of calculations has been described in detail in a recent publication addressing the SCLSs of all ordered O adlayers on Ru(0001) : Comparing with a large set of experimental high-resolution core-level shift data we achieved consistent agreement to within $`\pm 0.05`$ eV, confirming the high accuracy and predictive nature of our calculations.

However, we immediately stress that we do not expect such a precision when comparing metallic with oxidic core-levels. SCLSs are obtained from the difference between a surface and a bulk calculation and thus benefit from error cancelation, if both calculations are done on the same substrate (which eletronic structure may be equally well described by DFT-GGA) and within the same supercell. While this is obviously not the case for Ru vs. RuO2, notice that the focus of the present work is also not the explanation of a highly accurate existing data set on a very well defined sample. Rather, we intend to provide a fingerprint guidance for the XPS trends on an oxidizing Ru surface, where none of the conclusions drawn will be affected by a likely $`\pm 0.2`$ eV inaccuracy between the position of the Ru and RuO2 bulk peaks.

## III O$`(1\times 1)`$/Ru(0001) and RuO2(110) surface structure

The initial oxygen chemisorption on the Ru(0001) surface proceeds via four ordered adlayer structures, in which with increasing coverage O consecutively occupies the four available hcp sites of a $`(2\times 2)`$ unit cell . Sub-surface O penetration does not begin until the full O$`(1\times 1)`$ monolayer has been completed , which is why only the latter adphase may coexist with already fully oxidized patches under O-rich conditions . In the O$`(1\times 1)`$, every Ru surface atom, Ruchem,3f, is coordinated to three chemisorbed oxygens, Ochem, with a bondlength of 1.97 Å, cf. Fig. 1a. Note, that we will use a nomenclature for the surface Ru atoms, where apart from a site specific characterization (e.g. chem for the chemisorption phase) also the number of direct O neighbours (e.g. 3f for 3-fold coordination) is indicated. Vice versa, we indicate for the surface O atoms to which specific site they bind (e.g. Ochem binds to the Ruchem,3f atoms). In the rutile bulk structure of RuO2  the coordination is much higher compared to the chemisorption phase, albeit at a very similar bondlength: Every Ru atom is surrounded by an octahedron of six oxygens with O-Ru bondlengths of 2.00 Å and 1.96 Å to the four basal and two apical oxygens respectively. On the other hand, the Ru coordination of O atoms in the chemisorbed state and in the bulk oxide structure is both threefold.

If the rutile RuO2 is cut along the (110) plane, three distinct surface terminations are possible. The stoichiometric termination shown in Fig. 1b exhibits two types of atoms with truncated bonds, namely fivefold coordinated Rucus,5f and twofold coordinated Obridge atoms. As a result, both atoms relax inwards, which e.g. translates into a shortened bondlength of 1.91 Å between Obridge and the underlying sixfold coordinated Rubridge,6f atoms. This termination (henceforth referred to as Obridge termination) is traditionally believed to be the most stable one for (110) surfaces of all rutile-structured metal oxides , and in ultrahigh vacuum (UHV) it was also found on the oxide patches that had formed on the Ru(0001) surface . However, in recent calculations determining the lowest energy structure in equilibrium with a given environment we found that this termination is only stable at a low O chemical potential . Under more O-rich conditions a different termination (henceforth referred to as Ocus termination) is stabilized, in which terminal oxygen atoms, Ocus, occupy sites atop of the formerly coordinatively unsaturated Rucus,5f atoms as shown in Fig. 1c. Although this achieves the bulk-like sixfold O coordination for the now Rucus,6f atoms, the Ocus-Rucus,6f bondlength is due to the singly-bonded atop site with 1.70 Å significantly shorter than all aforementioned bondlengths in the O/Ru system.

By post-dosing the RuO2(110) surface with additional O at room temperature this high-pressure termination of RuO2(110) has recently also been created and characterized in UHV intentionally . However, depending on the details of the experimental preparation we are convinced that this high-pressure termination was probably also present in a number of previous studies addressing RuO2(110), in particular the ones where the oxide was treated under O-rich conditions without a final annealing step . We finally note in passing, that our calculations show that the third possibility of terminating a RuO2(110) crystal with a mixed (RuO) layer exhibited at the surface is never realized in the range of possible O chemical potentials.

## IV Results

### A Surface Core-Level Shifts for RuO2(110)

Aiming at a fingerprint guidance for XPS experiments, we concentrate on the discussion of the photoemission from those atoms, for which rather large SCLSs are expected due to a significantly changed local environment with respect to the bulk situation, cf. Table I and Fig. 1. From an inspection of the initial-state SCLSs we estimate that the peaks due to all other atoms, which are located in deeper surface layers, will lie closer than $`\pm `$ 0.2 eV around the respective RuO2 bulk peak. Note, that in our sign convention a positive SCLS indicates a shift towards higher binding energies, i.e. the core-level moves away from the Fermi level. Similarly, a positive screening contribution to the total shift occurs, if the created core hole is less screened at the surface than in the bulk.

Concentrating first on the Ru $`3d`$ SCLSs in the stoichiometric RuO2(110)-Obridge termination we find only rather modest shifts for both the Rubridge,6f and the Rucus,5f atoms. While this is not very surprising for the former atom, which possesses its sixfold bulk-like O coordination (albeit with a reduced bondlength to the Obridge atoms), one could have imagined a larger shift for the Rucus,5f atoms, which after all lack their atop apical oxygen neighbour. However, these atoms are considerably relaxed inwards, reinforcing the backbond to the underlying second apical O at a reduced bondlength of 1.88 Å. Thus, the bond truncation and backbond strengthening seem to balance up, leading in total to an almost bulk-like situation and in turn to a very small SCLS.

The final-state contribution for both atoms is negative, indicative of a more efficient screening at the surface. A similar screening behaviour was already found for all Ru surface atoms in the O adlayer phases on metallic Ru(0001) and explained by an enhanced $`d`$ density of states (DOS) around the Fermi level : Upon core excitation, the $`4d`$-band shifts to lower energies, causing a valence electron from the Fermi reservoir to restore local charge neutrality by filling up formerly unoccupied $`d`$-states. In turn, if the $`d`$-DOS at and above the Fermi level is higher for a surface atom than for a bulk atom, a more efficient screening results. Inspecting the $`d`$-DOS of both Rubridge,6f and Rucus,5f, we indeed find again such an enhancement, confirming that not only in the Ru metal, but also in its oxide the final-state effect is mainly due to intra-atomic $`d`$-electron screening.

In the RuO2(110)-Ocus termination, the Rubridge,6f SCLS remains almost unchanged, which is intelligible as the addition of the terminal Ocus atoms does not directly influence the nearest-neighbour coordination of this Ru surface atom, cf. Fig. 1c. However, the Rucus,6f atoms are of course significantly affected, exhibiting now a large shift of +1.37 eV towards higher binding energies. As apparent from Table I this shift is primarily an initial-state effect, which we attribute to the very short bondlength of 1.70 Å formed to the atop Ocus atoms. Yet, also the Rucus,6f $`d`$-DOS at the Fermi level is lowered so strongly by the new bond, that we additionally observe a sign reversal in the screening contribution. Reflecting a reduced screening capability at the surface the final-state effect points thus in the same direction as the large initial-state shift, further augmenting the total SCLS. Note, that we had previously observed such a change in the screening behaviour also at high coverage O adlayers on Rh(111), where the oxygen-metal interaction likewise reduced the $`d`$-DOS at the Fermi level below the corresponding bulk value . The resulting very large SCLS for the Rucus,6f atoms in this hitherto unaccounted high-pressure termination is related to a long standing controversy concerning the interpretation of XPS data on RuO2(110), which detailed discussion we defer to the following section.

Turning our attention to the O $`1s`$ shifts, we immediately recognize that contrary to the situation for the Ru $`3d`$’s, the total SCLSs are now predominantly determined by a large, negative screening contribution. The initial-state shifts on the other hand are almost bulk-like, with Obridge atoms showing very similar values in both terminations. The strongly enhanced screening at the surface is due to dangling-bond type states on both surface oxygens as reflected in the DOS shown in Fig. 2. These oxygen-metal states, which are concentrated on Obridge and Ocus and their respective directly bonded Rubridge,6f and Rucus,6f neighbours, fall in the energy region -8.0 eV $`<E<`$ -2.0 eV in bulk RuO2 , but are shifted towards the Fermi level due to the bond truncation at the surface. There they strongly enhance the DOS and thus induce the large negative screening contribution to the O $`1s`$ SCLSs.

### B The satellite peak discussion

Motivated by the widespread use of RuO2 as catalyst for electrochemical, as well as organic and inorganic processes, a large number of studies has already applied low-resolution XPS to elucidate the oxide’s surface structure and composition ( and references therein). Even at the resolution of a Mg/Al X-ray source the Ru $`3d`$ spectrum of RuO2(110) clearly shows an additional rather broad peak at about $`+1.7\pm 0.1`$ eV to the higher binding energy side of each of the primary 3/2 and 5/2 components . Under the assumption that the large shift of this peak indicates a significant deviation of the local environment of the emitting atom with respect to the bulk phase, the satellite was at first assigned to the presence of a higher oxidation state of Ru at the surface, namely Ru6+ in a RuO3 type oxide . Concomitantly, this interpretation resulted even in the inclusion of a Ru $`3d_{5/2}`$ binding energy for RuO3 in a common XPS handbook . However, more recent work has questioned the existence of this conjectured surface oxide, which is not known to be stable as a bulk phase . In particular, a recent analysis of XPD azimuthal scans by Kim et al. showed that the photoelectrons in the satellite peaks originate from a rutile-type environment , which is an unlikely structure for the presumed RuO3.

Alternatively, Cox et al.  attributed the satellite peak to final-state screening effects. As outlined in the previous section, the core hole created in the photoemission process pulls down formerly unoccupied valence band DOS below the Fermi level. The photoemission spectrum may then exhibit a multiple peak structure, often called the Kotani-Toyozawa effect : The high kinetic energy peak reflects the possibility that electron transfer into the shifted DOS happens fast enough to impart the corresponding screening energy onto the emitted photoelectron (this corresponds to the fully-screened results of our calculations). And the low-energy peak reflects the possibility that the shifted DOS remains unoccupied on the time scale of the emission process. Of course, in addition there is also the possibility of even lower kinetic energy structures than this “unscreened peak” because the emitted photoelectron may also loose energy, e.g. by creating surface plasmons. The Kotani-Toyozawa effect has been observed in photoemission from systems with highly localized $`f`$ or $`3d`$ valence band states . However, the good overlap and spatial extension of the $`4d`$ wavefunctions in RuO2 (the width of the shifted DOS peak is about 1 eV) suggests that the screening dynamics will be fast. Thus, the probability (i.e., the intensity) of this unscreened final-state peak should be low. Furthermore, our calculations show that the screening energy is small for emission from Ru core levels, cf. Table I. Thus, even if a Kotani-Toyozawa peak existed at the higher binding energy side, it would be shifted by less than 0.2 eV with respect to the peak due to the fully-screened final-state, which is not enough to account for the well separated satellite seen in the experiments.

On the other hand, for photoemission from the oxygen atoms, the dynamics of screening could be interesting: The nodeless O $`2p`$ states are very localized and the calculated screening energy is large. Consequently, the screened and unscreened surface peaks of the photoemission spectrum would be well separated. While the latter overlap (at least partly) with the bulk peak, the fully-screened final-state peaks are noticeably shifted to higher kinetic energy. Hence, high-resolution O $`1s`$ photoemission focusing on the low binding energy side of the bulk peak (i.e. the peak shape) could provide important information on the many-body dynamics of the photoemission process of this system.

Coming back to the Ru $`3d`$ satellite peak issue, we suggest in light of the SCLS analysis presented in the previous section, that it is neither due to RuO3, nor due to unscreened emission, but receives a signal from the Rucus,6f atoms in the RuO2(110)-Ocus high-pressure termination. Although the calculated large shift of +1.37 eV agrees at first sight only semiquantitatively with the experimentally reported $`1.7\pm 0.1`$ eV (cf. the compilation of measured XPS data in Ref. ), one has to keep in mind that all these studies were done with low-resolution XPS on rather ill-defined samples, the majority even on polycristalline material. In particular, none of the studies was performed on single-crystal RuO2(110), but always involving either oxidized Ru or grown RuO2 thin films, both bearing a certain likelihood for the presence of unoxidized Ru remnants on the surface. As we will show below, the metallic Ru bulk peak lies to the lower binding energy side of the RuO2 bulk peak, with all surface peaks due to Ru coordinated to chemisorbed oxygen in between. Unresolved, these peaks will lead to an erroneous RuO2 bulk peak determination at too low a binding energy and in turn to an overestimation of the total shift to the satellite peak, possibly explaining the 0.3 eV difference to our result.

Asides, the assignment of the satellite peak as a fingerprint for the hitherto simply not conceived high-pressure RuO2(110)-Ocus termination would be fully compatible with the reported experimental sample preparations, which unanimously involve highly oxidizing conditions. After the transfer to UHV the Ocus atoms are stable up to about 450 K , so that the high-pressure termination is most likely frozen in, if not a final annealing step is performed as e.g. in the LEED work by Over and coworkers . The Rucus,6f atoms in the RuO2(110)-Ocus termination are also obviously situated in a rutile-type environment, thus explaining the aforementioned XPD results of Kim et al. . Finally, we notice that our present model does not exclude the possibility that a many-body peak, e.g. due to a surface plasmon loss, falls in the same energy region, then being the predominant source of the satellite peak. At present, we can only state that the screened emission from Rucus,6f atoms - resolved or unresolved - contributes to the signal at the corresponding energy. Whether this is the sole explanation for the satellite peak or not, can only be determined by a high-resolution XPS study on single-crystalline RuO2(110), which we hope to encourage with the present work.

### C XPS fingerprinting of the oxidation sequence

Having completed the analysis of the oxidic SCLSs, we proceed to compare them with the peaks that arise from metallic Ru surface atoms coordinated to chemisorbed O. Since our intention focuses on describing the XPS trends during the oxidation of a Ru(0001) surface, we now reference all Ru $`3d`$ and O $`1s`$ SCLSs with respect to the initially present peaks due to bulk metallic Ru and chemisorbed Ochem,3f in the O$`(1\times 1)`$/Ru(0001) phase respectively. Again we stress that the shift between metallic and oxidic bulk peaks cannot be determined as accurately as the individual SCLSs on the respective surfaces and that we aim now more at the trends than at ironclad numbers. On the other hand, note that on a qualitative level our results even describe already the existing data from polycrystalline samples , Ru(0001) being the most stable surface orientation.

In our previous work addressing the ordered O overlayers on Ru(0001) we had shown that the progressive O chemisorption leads to a Ru $`3d`$ shift towards higher binding energies, which scales linearly with the number of direct O neighbours coordinated to the respective Ru surface atoms . For the final O$`(1\times 1)`$/Ru(0001), which in turn is precedent to and coexisting with already fully oxidized patches on an O-rich Ru(0001) surface , this results in a SCLS of +0.90 eV for the Ruchem,3f atoms as shown in Fig. 3a (cf. with the atomic structure displayed in Fig. 1a). On the contrary, we find the O $`1s`$ level almost constant to within +0.18 eV in all four adlayer structures, indicating that the always threefold coordinated Ochem,3f remains essentially in the same chemical state apart from a slightly increased repulsion due to the more and more close packing of the electronegative adsorbates in the higher coverage phases.

With the given accuracy caveat, we determine the Ru $`3d`$ peak due to bulk RuO2 at +0.46 eV on the higher binding energy side of the metallic Ru peak, which compares well with the polycristalline XPS literature value of $`+0.7\pm 0.1`$ eV . As apparent in Fig. 3b all Ru $`3d`$ peaks due to the UHV RuO2(110)-Obridge termination will thus fall between the Ruchem,3f peak due to the Ru surface atoms in the just described O$`(1\times 1)`$/Ru(0001) phase and the metallic Ru bulk peak. In contrast, emission from the Rucus,5f atoms in the RuO2(110)-Ocus termination will lead to the well separated satellite peak discussed in the previous section, cf. Fig. 3c, therewith offering a fingerprint for the existence of this domain type on the surface. With the presence of oxides on the surface the Ru $`3d`$ XPS spectrum will therefore clearly be shifted towards higher binding energies as more spectral weight is transferred to the oxidic peaks. Yet, even with a high-resolution X-ray source it will be very difficult to distinguish between coexisting RuO2(110)-Obridge and O$`(1\times 1)`$/Ru(0001) domains.

This distinction will be much more clearcut in the O $`1s`$ XPS spectrum. The peak due to RuO2 lattice oxygen appears at -0.64 eV towards lower binding energies, so that the largely shifted surface peaks of both oxide terminations show a total displacement of $``$ -1.5 eV. While this will thus not allow to determine which surface termination is present on the oxidic domains, the existence of the latter on the surface (even to a very small degree) will be easily monitored by the appearance of these new, well-separated peaks in the O $`1s`$ spectrum. Together with the Ru $`3d`$ satellite peak as a fingerprint for the high-pressure termination, all three domains should thus be clearly distinguishable by XPS, confirming our initial statement that the latter technique is a well suited tool to study the initial stages of the oxidation of the Ru(0001) surface.

## V Summary

The oxidation of the Ru(0001) surface proceeds via the O$`(1\times 1)`$ chemisorption phase before RuO2(110) domains start to form. From a calculation of the corresponding SCLSs we predict a shift of the Ru $`3d`$ (O $`1s`$) XPS spectrum towards higher (lower) binding energies as soon as oxide domains are present. In particular O $`1s`$ XPS will be a very sensitive tool to study the onset of the oxidation process, as the corresponding large shift results in the appearance of new peaks. The Ru $`3d`$ spectrum of RuO2(110) exhibits a clearly separated satellite peak at the higher binding energy side, which we assign to the existence of a hitherto unaccounted high-pressure termination. In this termination, terminal Ocus atoms sit atop of the formerly coordinatively unsaturated (cus) Rucus,5f atoms of the stoichiometric RuO2(110) termination, normally believed to be the most stable truncation of all rutile (110) crystals. The very short bondlength between the Ocus and Rucus,6f atoms significantly deviates from the bulk-like situation, leading to a large initial-state shift of the core-level of the latter and thus possibly causing the long disputed satellite peak.

## VI Acknowledgements

Stimulating discussions with Artur Böttcher and Horst Conrad are gratefully acknowledged.


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# Fourier Algebra of a Compact Lie Group

Let $`G`$ be a compact group and let $`A(G)`$ be the Fourier algebra of $`G`$. This is a commutative Banach algebra. As a Banach space, $`A(G)`$ is defined as the predual of $`vN(G)`$, the von Neumann algebra of $`G`$. Now weak amenability of $`A(G)`$ in the sense of  has been studied by Johnson , and we strengthen one of his results with the following result.

Theorem. Let $`G`$ be a compact connected Lie group. Then $`A(G)`$ is weakly amenable if and only if $`G`$ is abelian.

Proof (i) Let $`G`$ be abelian. Then the Pontryagin dual $`\widehat{G}`$ is a discrete abelian group. Then we have $`vN(G)\mathrm{}^{\mathrm{}}(\widehat{G})`$ and so we have

$$A(G)\mathrm{}^1(\widehat{G})$$

Now $`\mathrm{}^1(\widehat{G})`$ is amenable. Therefore $`A(G)`$ is weakly amenable.

(ii) Let $`G`$ be a non-abelian compact connected Lie group. For Lie groups our reference is Bourbaki  especially Lie IX.5 and Lie IX.31. The Lie algebra $`L(G)`$ decomposes as

$$L(G)=cD(L(G))$$

where $`c`$ is the centre of $`L(G)`$ and $`D(L(G))`$ is the derived algebra of $`L(G)`$. The derived algebra $`D(L(G))`$ is a semisimple Lie algebra. If $`G`$ is non-abelian then $`L(G)`$ is non-abelian and $`D(L(G))0`$.

Hence the root system

$$R(g_{},t_{})0$$

where $`g=L(G),t=L(T)`$ and $`T`$ is a maximal torus of $`G`$. But $`R(G,T)R(g_{},t_{})`$. Hence there exists a root $`\alpha R(G,T)`$.

Let $`Z_\alpha `$ be the centralizer of the kernel of $`\alpha `$. Let $`S_\alpha =D(Z_\alpha )`$ be the derived group (commutator subgroup) of $`Z_\alpha `$. Then $`S_\alpha `$ is a connected compact semisimple Lie group of rank 1.

Let $`\pi `$ be an irreducible representation of $`G`$ of degree $`d`$:

$$\pi :GU(d)$$

Consider $`TS_\alpha `$. This is a maximal torus of $`S_\alpha `$. There are only 2 possibilities for $`S_\alpha `$.

(i) $`S_\alpha =SU(2,)`$. Consider the restriction $`\pi |SU(2,)`$ and the fact that $`TS_\alpha `$ is a circle $`U(1)`$. Now

$$\pi |SU(2)=\lambda _1\mathrm{}\lambda _r$$

with each $`\lambda _1,\mathrm{},\lambda _r`$ irreducible. But $`\lambda _j|U(1)=\chi _m+\mathrm{}+\chi _m`$ where $`\chi _m(z)=z^m`$. Consequently we have $`|m|<d`$.

(ii) $`S_\alpha =SO(3,)`$. A similar argument gives $`|m|<d`$ for the characters occurring in $`\pi |U(1)`$.

We now apply the remark in Johnson (p.373) to infer that $`A(G)`$ is not weakly amenable.

Corollary. If $`G`$ is any compact connected Lie group except $`SO(2)`$ then $`A(G)`$ is not weakly amenable.

Mathematics Department, University of Manchester, Manchester M13 9PL, UK.


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# Strong Soret effect in one dimension

## I INTRODUCTION

When a binary fluid is subjected to a temperature gradient, the densities $`\rho _+`$ and $`\rho _{}`$ of the species become space-dependent in such a way that the relative concentration $`\rho _+(x)/\rho _{}(x)`$ changes along the direction of heat flow. This is the Ludwig-Soret, or Soret effect . That this effect happens does not in itself need an explanation: once the temperature difference takes the system away from equilibrium and breaks translational symmetry, there is no reason why the ratio of concentrations should stay constant.

However, the Soret effect has practical applications in the separation of species , and this requires a quantitative prediction of its magnitude in each case. There have been several analytic approaches to do this for gases , condensed phases , grains in suspension , porous media , etc. (For a review, see ).

From a purely theoretical point of view the Soret effect is interesting because it cannot in general be discussed in terms of local equilibrium, in which a space-dependent local temperature fully accounts for the concentration ratio — as for example the local pressure accounts for the variation of the density in a gas column under gravity. To see this explicitly, we consider here a model belonging to a family of systems for which such a local equilibrium approximation yields strictly zero effect, contrary to observation. They consist of two species of different masses $`m_+`$ and $`m_{}`$, interacting through a pair potential $`V(r_ir_j)`$ which does not depend on the particle type (the masses of particles $`i`$ and $`j`$). A short calculation shows that the partition function $`Z`$ of such a system is of the form:

$$\frac{1}{V}\mathrm{ln}Z(\rho _+,\rho _{},T)=\rho _+\mathrm{ln}\rho _+\rho _{}\mathrm{ln}\rho _{}+\frac{d}{2}\rho _+\mathrm{ln}(m_+T)+\frac{d}{2}\rho _{}\mathrm{ln}(m_{}T)\beta F(\rho ,T)$$
(1)
where $`F`$ depends on $`\rho _+`$, $`\rho _{}`$ only through their sum $`\rho \rho _++\rho _{}`$, and $`d`$ is the dimension. Assume now that under heat flow we can divide space in small cells $`\delta ^d(x)`$ with densities $`\rho _+(x)`$ and $`\rho _{}(x)`$, within which the system is in equilibrium at temperature $`T(x)`$. The total partition function will then be a product expressions (1) for each cell. If we now maximize it with respect to $`\rho _+(x)`$ and $`\rho _{}(x)`$ (with fixed number of particles) we get:

$`\alpha _+`$ $`=`$ $`{\displaystyle \frac{1}{T(x)}}{\displaystyle \frac{F}{\rho }}(\rho ,T(x))\mathrm{ln}(\rho _+)+{\displaystyle \frac{d}{2}}\mathrm{ln}(m_+)`$ (2)
$`\alpha _{}`$ $`=`$ $`{\displaystyle \frac{1}{T(x)}}{\displaystyle \frac{F}{\rho }}(\rho ,T(x))\mathrm{ln}(\rho _{})+{\displaystyle \frac{d}{2}}\mathrm{ln}(m_{})`$ (3)
with $`\alpha _\pm `$ space-independent Lagrange multipliers. Subtracting these equations we get $`\rho _+/\rho _{}=constant`$, i.e. no Soret effect.

In this paper we study a very simple one-dimensional model which belongs to the class described above, and has a most extreme form of Soret effect: there is total phase separation even for arbitrarily small temperature differences. The two pure phases are separated by an interface in which species are mixed, its width is a function of the parameters. Although this full separation is not realistic, it is interesting to exhibit a model which, for large sizes, is driven far from equilibrium by an arbitrarily small difference of temperature.

We also study in this model the closely related question of the laws for heat transfer. In regions in which phases are pure this transfer has an anomalous spatial and temperature dependence, just as found in oscillator chains . Within the interface we show that the behavior becomes the usual Fourier law, as recently found by Dhar  in a model similar to the present one, but in which particles are forced to stay mixed.

## II THE MODEL

We shall consider a one dimensional system of length $`L`$ consisting of $`N`$ point particles of two species: $`N_+`$ heavy and $`N_{}`$ light particles of masses $`m_+`$ and $`m_{}`$, respectively.

Particles interact through an infinitely narrow potential of height $`V`$, so that when two particles meet they collide if their center of mass energy

$$E_c=\frac{1}{2}\frac{m_1m_2}{m_1+m_2}(v_1v_2)^2<V$$
(4)
and ignore each other otherwise. The collision between particles conserves energy and momentum:

$$v_1v_1^{}=v_1+\frac{2m_2}{m_1+m_2}(v_2v_1)$$
(5)
$$v_2v_2^{}=v_2\frac{2m_1}{m_1+m_2}(v_2v_1)$$
(6)
These collision rules are reversible and satisfy detailed balance. Between collisions the particles evolve freely across the system. Particles colliding against the walls $`x=0`$ and $`x=L`$ rebounce with a velocity with random distribution corresponding to thermalisation at temperatures $`T_c`$ and $`T_h`$, respectively:

$$P_\alpha (v)dv=\frac{m}{\kappa T_\alpha }v\mathrm{exp}\left(\frac{mv^2}{2\kappa T_\alpha }\right)dv\alpha =c,h$$
(7)
This guarantees that if $`T_c=T_h`$ the system equilibrates to the Maxwell distribution.

In fact, only the potential between particles of different species is relevant, since particles of equal mass only exchange their velocities in a collision, which then just amounts to exchanging their labels — a one dimensional peculiarity. As a consequence of this, we can consider this model as having a potential $`V(r_ir_j)`$ which is independent of particle type (and hence belongs to the family (1)), and at the same time consider that particles of the same type are transparent to one another, and hence our model is a particular case of the one introduced by Widom and Rowlinson.

## III PHASE SEPARATION

We use a simple molecular dynamics in the simulation, calculating the minimum collision time and letting the system evolve freely between collisions. We perform simulations for different number of densities, and different values of the length ranging from $`L=100`$ to $`L=2000`$, which allows us to consider finite-size effects.

We have checked that in the equilibrium case (the temperature in both sides of the system are identical) the two species are homogeneously distributed in space and their velocity distribution is Maxwellian. We also have checked that for the case of one type of particles with two different temperatures, the average energy is the one corresponding to an homogeneous temperature $`\sqrt{T_cT_h}`$. This is because if we consider only one type of particles, in the elastic case the particles simply cross the system without any interaction with other particles and it is easy to verify that the distribution of velocities is just composed of two Maxwellian distributions at different temperatures for particles flying in each direction.

In Fig.1 we show the evolution of the particles after a long thermalisation time, starting from a configuration with random positions ($`L=100`$, $`V/T_c=10`$, $`T=T_h/T_c=10`$, $`m_{}/m_+=0.2`$). We can see that the space is divided in two regions with only a single species, separated by an interface in which both species mix. Away from the interface, because all particles have the same mass, the system can be considered as non-interacting. Hence we have the following picture: the heavy particles collide with the hot wall at $`x=L`$. They fly unperturbed (modulo relabelings) throughout the the heavy-particle phase, until they meet the first light particles around the interface. After one or more crossings and collisions with light particles, they return to the heavy-particle phase, where they are free again. The same can be said of the light particles on the left.

A simple computation helps clarify what happens in the interface. Consider a system with a light and a heavy particle. Estimating their velocities according to the temperatures of the walls, we have:

* If the light particle is on the left and the heavy one on the right:

$$v_{}^2\frac{T_c}{m_{}}v_+^2\frac{T_h}{m_+},$$
(8)
which gives a typical center of mass energy:

$$2E_{CM}^{(1)}=\frac{(T_c+T_h)(m_++m_{})(\sqrt{T_cm_{}}+\sqrt{T_hm_+})^2}{(m_++m_{})}.$$
(9)
* If the heavy particle is on the left and the light one on the right:

$$v_{}^2\frac{T_h}{m_{}}v_+^2\frac{T_c}{m_+},$$
(10)
giving the typical precollision center of mass energy:

$$2E_{CM}^{(2)}=\frac{(T_c+T_h)(m_++m_{})(\sqrt{T_hm_{}}+\sqrt{T_cm_+})^2}{(m_++m_{})}$$
(11)

In fact is easy to show that:

$$A=\frac{2E_{CM}^{(1)}}{2E_{CM}^{(2)}}<1\mathrm{if}m_+>m_{};T_c<T_h,$$
(12)
Hence, we see that the probabilities of collision are not symmetric: while this does not prove that phase separation exists, it gives us the sign of the effect. Note that there is a similarity with asymmetric exclusion processes , although unlike that case here detailed balance holds in the bulk.

## IV INTERFACE

In Fig.2 we show the time-averaged particle densities $`\rho _+(x)`$ and $`\rho _{}(x)`$:

$$\rho _\pm (x)=1/t\underset{t\mathrm{}}{lim}_0^t𝑑t^{}\underset{i\pm }{}\delta (xx_i(t^{}))$$
(13)
for a system with the same parameters as Fig.1. We see, as before, that the two types of particles are completely separated, but the interface seems much thicker than in Fig.1. The reason for this discrepancy is simple: the position of the interface fluctuates with time. Upon time-averaging we are actually measuring the instantaneous interface width convoluted with the dispersion in its position.

The fluctuations in the position of the interface $`\mathrm{\Delta }L`$ scale with the system size $`L`$. In Fig.3 we check the assumption that, just like in an ordinary equilibrium system $`\mathrm{\Delta }L\sqrt{L}`$. In order to do this, we plot the product of densities $`\rho _+(x)\rho _{}(x)`$, a quantity that is large only in the interface, for several system sizes and we verify that, indeed, the function scales with $`\sqrt{L}`$. In 3 we have considered again the same parameters as in Figs.1 and 2, and systems lengths from $`L=100`$ to $`L=800`$. Rescaling the averaged interface with $`\sqrt{L}`$, the curves collapse.

In Figures 4 we plot $`\rho _+\rho _{}`$ for a system of length 100 and $`V=10`$. On the left figure we vary the temperature of the hot wall keeping the mass ratio constant, while on the right figure we have changed the mass ratio while keeping the temperatures constant. These plots show us the shift in terms of the parameters of the average location of the wall.

As we seen above, the time-averaged width of the interface is dominated by the time fluctuations of the wall position, rather than by its instantaneous width. Hence, it is convenient to define a parameter that reflects the mixing of the particles at every time, thus giving a measure of the instantaneous width of the interface. For each heavy particle we count the number $`q_i`$ ($`=0,1,2`$) of its nearest neighbors that are light particles. Our parameter is then:

$$q\frac{_i^Nq_i1}{2}$$
(14)
For a sharp interface $`q=0`$, and for a very mixed system $`q`$ is of order $`N`$. In Fig.5 we show the frequency distribution of $`q`$ averaged over many time-steps for various sizes of the system. We see that the averaged distribution of $`q`$ (which reflects the instantaneous width of the interface) is independent of the system size, as expected. We can hence study how the width changes with the various parameters, in a system-size independent way.

On (a) we can see how the sharpness of the interface increases as we decrease the mass ratio. The same effect occurs when we increase the interaction potential (b) or the temperature ratio (c). The physical interpretation of these tendencies is easy to understand. The system is completely mixed when the two thermal walls are at the same temperature. In fact, in this case the asymmetry (12) in the probability of collisions disappears ($`A=1`$), and equilibrium is reached. Obviously if the masses are equal or the interaction potential is zero, the system is also completely mixed because there are no collisions.

We have found no evidence of a threshold in the values below which there is no separation for an infinite system. Indeed, the limit of ‘mixed particles’ (e.g. at equal temperatures or equal masses) is only achieved when the interface length becomes larger than system size.

## V BOLTZMANN EQUATION

Let us now write down a Boltzmann equation for the probability distribution function of the velocities of the particles, and check that it reproduces correctly the phase-separation effect.

We have to deal with two coupled equations:

$$\frac{f(x,v,t)}{t}=v\frac{f}{x}+|vu|(f(x,v^{},t)g(x,u^{},t)f(x,v,t)g(x,u,t))𝑑u$$
(15)
$$\frac{g(x,v,t)}{t}=v\frac{g}{x}+|vu|(f(x,u^{},t)g(x,v^{},t)f(x,u,t)g(x,v,t))𝑑u$$
(16)
where $`f(x,v,t)`$ and $`g(x,v,t)`$ are the probability distributions for the two types of particles. As usual, $`u^{}`$ and $`v^{}`$ are velocities the particles should have before the collision in order that the velocities after collision are $`u`$ and $`v`$ respectively. These equations must be solved with the adequate boundary conditions (7). In this equations we have omitted the interaction potential, in fact there would be a $`\mathrm{\Theta }`$-function which guarantees the collision.

The approximation that is made in equations (15) and (16) is that the correlations between particles are neglected: each particle collision is independent of the collisions the particle has suffered before. More formally, this means that:

$`f_2(x,x^{},v,v^{},t)=f(x,v,t)f(x^{},v^{},t)`$ (17)
$`g_2(x,x^{},v,v^{},t)=g(x,v,t)g(x^{},v^{},t)`$ (18)
Unfortunately, as far as we know, the system (15) and (16) cannot be solved analytically. We solve it numerically using a stochastic process based on the Bird algorithm  which has been proved  to converge to the solution of the Boltzmann equation. We have used this algorithm for this system taking into account the delta-like potential.

In Fig.7 we show the profile of the spatial density of the two types of particles for a system consisting of 200 particles of each type for a potential $`V/T_c=4`$, mass ratio $`m_+/m_{}=0.2`$ and temperature ratio $`T_h/T_c=10`$. We can see that the two normalized profiles are almost identical, which confirms the validity of the Boltzmann approximation. This good agreement holds for any value of the parameters.

The fact that the Boltzmann equation is a good approximation, at least away from the interface, is easy to understand. As the two species are separated, the most likely situation after a collision is that at least one of the two colliding particles goes freely to its corresponding wall, it loses all memory of the correlation with other particles. Thus, the neglect of the correlations implicit in the Boltzmann equation is a good approximation.

A special note should be made about the interface fluctuations. The Boltzmann equation has a unique solution for every finite length $`L`$ (it is first order). However, if we were to compute the stability matrix around the solution, we would find that the mode corresponding to translation of the wall becomes softer as $`L\mathrm{}`$. This in turn means that corrections to the Boltzmann approximation become more and more important in that limit, and they yield the wall’s fluctuations. (This question becomes more familiar if we bear in mind the analogy with a 2D Ising ferromagnet with the spins on right boundary set to $`+1`$ and on the left to $`1`$. The Boltzmann equation is analogous to a mean-field solution, which places the interface in the middle, and neglects the fluctuating displacements of the domain wall.)

## VI HEAT TRANSPORT - RECOVERY OF FOURIER LAW FOR BROAD INTERFACE

In one dimensional systems, the obtention of Fourier’s law is still an open question . As mentioned above, this one dimensional model has the peculiarity that particles can be considered non-interacting everywhere except in the interface, where both species mix. This reflects itself in an extremely pathological form of heat transfer: the only spatial gradient in kinetic energy of the particles occurs across the interface, since far from the interface we have a gas of noninteracting particles. It thus seems reasonable, if we wish to recover the usual laws for heat transfer, to place ourself in conditions such that the interface is broader than the sample itself and species are mixed.

In order to study the temperature profile in the interface we have chosen very small temperature differences and species with very similar masses. In Fig.8 we show the energy profile for a system of length $`L=100`$ with $`100`$ particles of each type, with masses $`m_+=1`$ and $`m_{}=0.95`$, respectively. We plot the energy profile for $`m_+`$ for different values of the temperature ratio, $`T_h/T_c`$= 1.05, 1.10, 1.15, 1.20. We can clearly see that the energy distribution changes linearly along the system, and that it is proportional to the thermal gradient. In fact, the straight lines fitted have all the same slope, indicating that the conductivity in the interface is the same for all cases.

Even in this small gradient case we can see that the mass distribution is not uniform. In fact, the massive particles are located closer to the hottest wall while the lightest ones are closer to the coldest wall. This fact can be seen in Fig.9, where we have plotted the normalized particle densities for the same case as in Fig.8 for $`T_h/T_c=1.30`$. Note that the mass profile is also linear in small thermal gradients.

The fact that we have found the Fourier Law for the broad-interface case is not surprising, in view of the similar result of Dhar  mentioned in the introduction. Note, however, that unlike the present situation, in Ref.  particles with different masses are never allowed to cross, so the Soret effect is avoided completely.

It can also be seen that for a fixed small thermal gradient, the temperature profile depends linearly on the difference of masses. This fact suggests the possibility of expanding the Boltzmann equation in powers of this parameter and making an estimation of the conductivity for the case in which the masses of the two species are very similar  .

## VII CONCLUSIONS

In this paper we have numerically solved a model with two types of particles with different masses. We have shown that a thermal gradient is enough to separate completely the two species, at least if the system is large enough to accommodate the interface. The phase separation is due to the collision asymmetry (12) provoked by the thermal gradient applied. For large enough systems, the heavy particles are closer to the hottest wall while the light particles are closer to the coldest one. Between these two regions there is an interface where the two types of particles live together. In the regions occupied by only one type of particles the kinetic energy gradient is zero because the system is a noninteracting gas, so that all the energy density drop is localized in the interface (a finite region of the space). We have also studied the behavior of the interface for different values of the characteristic parameters of the system, showing that its instantaneous width is independent of the system size. By means of a numerical solution of the Boltzmann equation for this systems, we have checked that the total phase separation is also obtained within this approximation (equations (15),(16)). We have also investigated the limit of ‘broad interface’, in which the interface is broader than the system itself, and shown that Fourier’s Law is recovered in that case.

To sum up, we have introduced a very simple one dimensional model which has an extreme Soret effect for an infinite system, while in a finite system reproduces not only Fourier’s Law but also a linear distribution of densities along the system.

ACKNOWLEDGMENTS

We wish to thank B. Derrida, J. Lebowitz, M. Martin, R. Livi, M. Rubi, S. Ruffo, and J-E Wesfreid for useful suggestions and discussions. We also thank I. Pagonabarraga for a careful reading of the manuscript.


text:
# Hall effect in underdoped GdBa2Cu3O7-δ thin films: evidence for a crossover line in the pseudogap regime.

## I Introduction

Among the anomalous normal state transport properties observed in high temperature superconductors, the temperature dependence of the Hall constant is probably one of the most striking: it displays a behavior which is totally different from the one observed in simple metals. Indeed, it is generally observed, in particular in REBa2Cu3O7-δ (RE rare earth) compounds, that the temperature dependence of the Hall coefficient, $`R_H(T)`$, goes as $`1/T`$ over a wide temperature range and presents an ill-understood peak above $`T_c`$, whereas the cotangent of the Hall angle ($`\mathrm{cot}(\theta _H)=\rho _{xx}/\rho _{xy}`$ where $`\rho _{xx}`$ and $`\rho _{xy}`$ are respectively the longitudinal and Hall resistivity) varies as $`T^2`$ over a wide temperature range. One way to analyze the temperature dependence of the Hall effect is to consider two different relaxation rates. Experimental reports , showing that the cotangent of the Hall angle obeys a $`T^2`$ law even if $`R_H^1(T)`$ or $`\rho _{xx}(T)`$ are strongly nonlinear suggest that the cotangent of the Hall angle is a function of a single relaxation rate, $`\tau _H^1`$, whereas the resistivity $`\rho _{xx}`$ would be related to another relaxation rate $`\tau _{tr}^1`$. Other scenarios based on a temperature dependent carrier concentration or on a scattering time that depends on the Fermi surface location have been proposed. When considering two relaxation rates, the Hall constant $`R_H`$ depends on both $`\tau _H`$ and $`\tau _{tr}`$: $`R_H^1=\mathrm{cot}(\theta _H)H/\rho _{xx}\tau _H^1/\tau _{tr}^1`$. The $`T^2`$ temperature dependence of the cotangent of the Hall angle, $`\mathrm{cot}(\theta _H)=AT^2+C`$, has been theoretically predicted , and observed experimentally in many systems . In the approach proposed by Anderson  the two scattering rates reflect spin and charge separation with the Hall angle being directly related to the spinon relaxation rate. In this view, magnetic impurities bring another scattering channel for the spinons and thus directly affect the behavior of the Hall angle as first observed experimentally by T. R. Chien, Z. Z. Wang and N. P. Ong .

Recent experimental results and theoretical ideas on the nature of the pseudogap  and its influence on Hall measurements , the possible presence of charge inhomogeneities , or the presence of vortex like excitations in the pseudogap phase  have changed our view of the normal state. In this paper, we revisit the question of the Hall effect by measuring the Hall constant and the Hall angle in the pseudogap phase of epitaxial underdoped GdBa2Cu3O7-δ films. The results are presented and discussed in the context of the recent findings mentioned above.

## II Samples and experiment

A series of GdBa2Cu3O7-δ thin films were grown by off-axis magnetron sputtering on (100) SrTiO3 substrates. The temperature of the substrates was typically $`700^{}C`$, and the $`Ar+O_2`$ sputtering pressure $`0.15Torr`$ $`(O_2/Ar=0.4)`$.  The oxygen content in the films was changed by varying the oxygen pressure during the cooling procedure . The structural crystalline quality of the films was checked by x-ray diffraction analysis. $`\theta 2\theta `$ and phi scans indicate an epitaxial growth with the $`c`$ axis oriented perpendicular to the substrate surface. Low angle x-ray reflectivity oscillations as well as finite size effects around the 001 peaks allow determination of the individual sample thickness, which was varied from $`20`$ to $`60nm`$ in this study. To prevent degradation during the lithographic processes, the films were protected by the subsequent in-situ deposition of an amorphous insulating layer. All the samples were photolithographically patterned using ion milling with a $`100\mu m`$ bridge wide. The relatively low thickness of the films allowed us to increase the measured voltages and to reduce the noise of the measurements. The $`dc`$ Hall voltage was measured using a three voltage contact technique and by adjusting the Hall voltage to zero in zero magnetic field. At each temperature, the Hall voltage was measured by sweeping the magnetic field between $`6`$ and $`+6`$ Tesla. During each measurement, the temperature, measured with a cernox resistance, whose magnetoresistance is negligibly small, was stable within $`\pm `$ $`5mK`$.

## III Results and discussion

Figure 1 shows the Hall constant $`R_H`$, as a function of temperature, for a series of GdBa2Cu3O7-δ thin films. On Fig. 1 the curves correspond to films with critical temperatures of $`84.6K`$, $`80.9K`$, $`79.0K`$, $`62.7K`$, $`48.9K`$ and $`53.1K`$. As can be seen, $`T_c`$ \[Ref.\] scales with the inverse Hall coefficient $`R_H^1`$. Since $`R_H^1`$ depends on the temperature, the relation between the doping level and $`R_H^1`$ is not straightforward. Here, we will simply use, as others , the value of $`R_H^1`$ at 100 $`K`$ as a parameter related to the doping level. We find that the $`T_c`$ versus $`R_H^1(100K)`$ curve obtained is in good agreement with YBa2Cu3O7-δ single crystals data. This observation is consistent with a $`T_c`$ reduction and a change in doping in these thin films essentially related to a change in oxygen content. In Fig. 1 the highest $`T_c`$ sample has a resistivity which is typically twice the value found in optimally doped thin films . The value of $`R_H^1(100K)`$ for this same sample is slightly less than half the value found in optimally doped thin films , implying that, in this thickness range, our films are not fully oxidized . One can also notice on Fig. 1 that the maximum in $`R_H`$ occurs in the normal state around $`100K`$ for each sample and does not seem to be related to the $`T_c`$ of the sample. This point will be discussed below in detail.

In Fig. 2 the temperature dependence of $`R_H^1`$ is shown for four representative samples. For the almost optimally doped sample with $`T_c=84.7K`$, $`R_H^1`$ is linear in temperature over a wide temperature range as observed experimentally in optimally doped YBa2Cu3O7-δ crystals . The temperature at which the inverse Hall constant deviates from linearity is shown by an arrow for each sample. For the highest $`T_c`$ sample the deviation in linearity is found to be very close to the peak in $`R_H`$ (minimum of $`R_H^1`$). For more underdoped samples, the temperature at which the deviation occurs is shifted, the lower the $`T_c`$, the higher this temperature. These data are found to be consistent with the results of R. Jin and H. R. Ott  who made a systematic study of the Hall effect on YBa2Cu3O7-δ single crystals. They found that the temperature at which $`R_H^1`$ deviates from linearity is in good agreement with the temperature at which anomalies in the temperature dependence of other physical properties are reported, these anomalies being associated with the opening of the pseudogap at the temperature $`T^{}`$.

We turn now to the analysis of the behavior of $`\mathrm{cot}(\theta _H)`$. Figure 3 shows for four selected samples $`(\mathrm{cot}(\theta _H)C)/T^2`$ and $`R_H`$ as a function of temperature. Our data on the temperature dependence of $`\mathrm{cot}(\theta _H)`$ show, over a temperature range extending from $`100K`$ to $`300K`$, a perfect $`T^2`$ dependence for all the doping levels investigated. No anomalies at temperatures close to $`T^{}`$ (or at the temperature at which $`R_H^1(T)`$ deviates from linearity) are found in $`\mathrm{cot}(\theta _H)(T)`$. As shown in Fig. 3, $`(\mathrm{cot}(\theta _H)C)/T^2`$ is temperature independent for all the samples until a characteristic temperature at which a deviation is observed. We notice, as apparent on Fig. 3, that this temperature is essentially not affected by the sensitivity criterium used to define the deviation in the $`T^2`$ temperature dependence of $`\mathrm{cot}(\theta _H)`$. As can be seen also in Fig. 3, this second characteristic temperature $`T^{^{}}`$, is well correlated with the temperature at which $`R_H`$ displays a peak and is almost independent of the doping level in the range investigated. At this temperature $`T^{^{}}`$ no anomaly is observed in the resistivity, the peak in $`R_H(\rho _{xx}/\mathrm{cot}(\theta _H))`$ has to be attributed to the change in $`\mathrm{cot}(\theta _H)(T)`$.

Since no deviation in $`\mathrm{cot}(\theta _H)`$ is observed at high temperature (close to $`T^{}`$), we conclude in the two relaxation times picture, that the deviation in $`R_H^1=\mathrm{cot}(\theta _H)H/\rho _{xx}\tau _H^1/\tau _{tr}^1`$ has to be attributed to a change in $`\tau _{tr}^1`$, a diminution of the scattering rate related to the opening of the pseudogap. Since $`\rho _{xx}\tau _{tr}^1`$, a deviation from the linear temperature dependence of the resistivity should be observed at the same characteristic temperature. A detailed analysis of the resistivity is difficult however, since, as often observed in underdoped thin films, the resistivity is not linear with temperature in this temperature range. It should be noticed that the $`T^2`$ temperature dependence of $`\mathrm{cot}(\theta _H)`$ is observed up to temperatures much higher than $`T^{}`$ implying that the mechanism at the origin of the $`T^2`$ behavior extends at temperatures above the pseudogap phase.

In Fig. 4, we present a phase diagram $`T`$ versus $`R_H^1(100K)`$ that summarizes the results of the paper. First $`T_c`$ versus $`R_H^1(100K)`$ is plotted (squares) along with single crystals data (circles). The line is a guide to the eyes. As can be seen the critical temperatures of films and crystals fall on the same curve. The temperatures at which a deviation in the linear temperature dependence of $`R_H^1(T)`$ is observed are indicated by triangles. These points follow the temperature dependence of the pseudogap temperature $`T^{}`$ as discussed above. Finally, the diamonds are the well defined temperatures $`T^{^{}}`$ at which a deviation in the $`T^2`$ behavior of $`\mathrm{cot}(\theta _H)`$ occurs (or at which $`R_H`$ is maximum). $`T^{^{}}`$ falls between $`T_c`$ and $`T^{}`$, clearly separating the pseudogap phase in two regions.

Before discussing this phase diagram and in particular the temperature $`T^{^{}}`$, one can compare these results to very recent experiments on Bi2Sr2Can-1CunOy films  which focalize on the doping dependence of the Hall response. In this system Z. Konstantinović, Z. Z. Li and H. Raffy do not observe a correlation between the peak in $`R_H`$ and the deviation in $`\mathrm{cot}(\theta _H)`$. Their data, however, show that the temperature at which a deviation in $`\mathrm{cot}(\theta _H)(T)`$ occurs is much lower than $`T^{}`$, in agreement with the data presented here. We can also relate our data to other recent experimental findings. Analysis of the temperature dependence of $`R_H(T)`$ have suggested that the peak in $`R_H(T)`$ is related to the pseudogap . It is however clear from the experimental data shown in Fig. 4, that the temperature of the maximum in $`R_H`$ is well defined and does not follow the pseudogap temperature dependence, suggesting that the latter is not, at least directly, responsible for the behavior observed.

There have also been reports on Bi2Sr2CaCu2O8+δ and La2-xSrxCuO4 compounds of the presence of vortex like excitations in the pseudogap phase. High frequency conductivity experiments  and measurements of the Nernst effect  have shown that vortex like excitations are found at temperatures up to $`100150K`$. Although measured on different systems, these temperatures are above $`T_c`$ but below the pseudogap temperature $`T^{}`$, as the characteristic temperatures $`T^{^{}}`$ measured in this work. Since experimentally  without implying a particular scenario, the Hall angle has been shown to be sensitive to magnetic impurities through $`\tau _H^1`$, an interesting possibility is that vortex like excitations may affect the Hall angle. These vortex like excitations could be seen as a parallel, temperature dependent channel for magnetic scattering modifying the Hall angle and indirectly $`R_H`$. The enhancement of $`\mathrm{cot}(\theta _H)`$ due to this additional scattering source would be responsible, in this system for the break in the temperature dependence of $`R_H`$.

The Nernst effect experiments, the high frequency experiments and the Hall data shown here point to a new crossover in the phase diagram. From an experimental point of view, three crossover temperatures are thus observed in underdoped cuprates: from weak ($`T_0`$) to strong pseudogap at $`T^{}`$ and, at lower temperature, the ”new” crossover line discussed above. The crossover from weak to strong pseudogap has been intensively discussed in the literature theoretically and experimentally. Several theoretical approaches have been suggesting or calculating the existence of an additional structure in the strong pseudogap phase. In particular, phase diagrams with a new temperature $`T_{charge}`$ at which charge ordering occurs have been discussed in the presence of charge inhomogeneities or stripes. Experimentally, T. Noda, H. Eisaki and S. Uchida have measured the Hall effect in La2-x-yNdySrxCuO4 \[Ref. \] and have related the sharp decrease in $`R_H`$ to one dimensional charge transport . We note also that recently, P. Devillard and J. Ranninger have predicted that there should exist a new characteristic temperature $`T_B^{}`$ in the pseudogap phase, between $`T^{}`$ and $`T_c`$, that corresponds to the temperature at which the electron pairs, formed at higher temperature ($`T^{}`$), become itinerant, defining an upper limit for partial Meissner screening  (and vortex like excitations).

There are perhaps two main tentative theoretical frameworks for the pseudogap regime. In one, the pseudogap state is fluctuating superconductivity: the system is superconducting over short distances and time scales, but phase fluctuations destroy the long range superconducting order. The second main theoretical framework is related to the proximity of these systems to Mott insulators, and attempts to describe these strongly correlated systems with various schemes of spin charge separation or gauge theories. The Hall effect experiments presented in this paper raise in fact two related questions. Firstly whether the difference between the Hall and the resistivity temperature dependencies entails the existence of two different relaxation mechanisms and times, or whether it should be explained in a different way. If two different scattering times do indeed characterize the Hall effect situation in high temperature superconductors, then one must somehow reconcile this fact with the existence of the lower crossover. Unfortunately, the various spin charge separation theories, that provide in principle a natural explanation for the different relaxation times, have up to now, to our knowledge, not predicted a second crossover in the strong pseudogap regime. This difficulty could possibly be resolved if one assumes that the holons or chargons behave as 2D bosons: the new temperature $`T^{^{}}`$ could then be the critical temperature of the corresponding 3D system as recently discussed by Y. J. Uemura in the context of ”preformed pairs”. On the other hand, if the lower crossover is connected with the loss of short distance phase coherence between ”preformed pairs”, and therefore the disappearance of vortices, one is left in this phase fluctuation picture with the problem of finding a mechanism for the existence of two different relaxation times, and this, way above $`T^{}`$.

## IV Conclusion

In conclusion, we have studied the transport properties, resistivity and Hall effect, in a series of underdoped GdBa2Cu3O7-δ epitaxial thin films, grown by off-axis magnetron sputtering. We find that the inverse Hall constant is linear over a temperature range that decreases as $`T_c`$ decreases. The temperature at which a deviation in $`R_H^1`$ occurs is close to the pseudogap temperature $`T^{}`$ measured in this material. We also find that $`\mathrm{cot}(\theta _H)`$ displays a perfect $`T^2`$ temperature dependence over a large temperature range extending from about $`100K`$ to $`300K`$. We observe for all the samples that the temperature at which the temperature dependence of the Hall angle deviates from the $`T^2`$ behavior is precisely correlated to the temperature at which $`R_H`$ displays a peak. This characteristic temperature, found to lie between $`T_c`$ and the pseudogap temperature $`T^{}`$, does not depend markedly on the doping level and defines a new crossover in the phase diagram.

We thank Z. Te$`\stackrel{˘}{\mathrm{s}}`$anović for bringing to our attention the possible importance of vortices in the pseudogap phase, D. Marré for help in the initial stage of this project and D. Chablaix for technical help. This work was supported by Swiss National Science Foundation.


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# Realization of Bose-Einstein condensates in lower dimensions

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## Abstract

Bose-Einstein condensates of sodium atoms have been prepared in optical and magnetic traps in which the energy-level spacing in one or two dimensions exceeds the interaction energy between atoms, realizing condensates of lower dimensionality. The cross-over into two-dimensional and one-dimensional condensates was observed by a change in aspect ratio and saturation of the release energy when the number of trapped atoms was reduced.

\]

New physics can be explored when the hierarchy of physical parameters changes. This is evident in dilute gases, where the onset of Bose-Einstein condensation occurs when the thermal deBroglie wavelength becomes longer than the average distance between atoms. Dilute-gas condensates of density $`n`$ in axially-symmetric traps are characterized by four length scales: Their radius $`R_{}`$, their axial half-length $`R_z`$, the scattering length $`a`$ which parameterizes the strength of the two-body interaction, and the healing length $`\xi =(4\pi na)^{1/2}`$. In almost all experiments on Bose-Einstein condensates, both the radius and length are determined by the interaction between the atoms and thus, $`R_{},R_z\xi a`$. In this regime, a BEC is three-dimensional and is well-described by the so-called Thomas-Fermi approximation . A qualitatively different behavior of a BEC is expected when the healing length is larger than either $`R_{}`$ or $`R_z`$ since then the condensate becomes restricted to one or two dimensions, respectively. New phenomena that may be observed in this regime are for example quasi-condensates  and a Tonk’s gas of impenetrable bosons .

In this Letter, we report the experimental realization of cigar-shaped one-dimensional condensates with $`R_z>\xi >R_{}`$ and disk-shaped two-dimensional condensates with $`R_{}>\xi >R_z`$. The cross-over from 3D to 1D or 2D was explored by reducing the number of atoms in condensates which were trapped in highly elongated magnetic traps (1D) and disk-shaped optical traps (2D) and measuring the release energy. In harmonic traps, lower dimensionality is reached when $`\mu _{3D}=4\pi \mathrm{}^2an/m<\mathrm{}\omega _t`$. Here, $`\omega _t`$ is the trapping frequency in the tightly confining dimension(s) and $`\mu _{3D}`$ is the interaction energy of a weakly interacting BEC, which in 3D corresponds to the chemical potential. Other experiments in which the interaction energy was comparable to the level spacing of the confining potential include condensates in one-dimensional optical lattices  and the cross-over to an ideal-gas (zero-D) condensate , both at relatively low numbers of condensate atoms.

Naturally, the number of interacting atoms in a lower-dimensional condensate is limited. The peak interaction energy of a 3D condensate of $`N`$ atoms with mass $`m`$ is given by $`\mu _{3D}=\mathrm{}^2/2m(15Na/l_z^2l_{}^4)^{2/5}`$, where $`l_{,z}=(\mathrm{}/m\omega _{,z})^{1/2}`$ are the oscillator lengths of the harmonic potential. The cross-over to 1D and 2D, defined by $`\mu _{3D}=\mathrm{}\omega _t`$ or equivalently $`\xi =l_t`$ occurs if the number of condensate atoms becomes

$`N_{1D}=\sqrt{{\displaystyle \frac{32\mathrm{}}{225ma^2}}}\sqrt{{\displaystyle \frac{\omega _{}}{\omega _z^2}}}=\sqrt{{\displaystyle \frac{\omega _{}}{\omega _z^2}}}\times 7200\sqrt{{\displaystyle \frac{\mathrm{rad}}{\mathrm{s}}}}`$ (1)
$`N_{2D}=\sqrt{{\displaystyle \frac{32\mathrm{}}{225ma^2}}}\sqrt{{\displaystyle \frac{\omega _z^3}{\omega _{}^4}}}=\sqrt{{\displaystyle \frac{\omega _z^3}{\omega _{}^4}}}\times 7200\sqrt{{\displaystyle \frac{\mathrm{rad}}{\mathrm{s}}}},`$ (2)
where we have used the scattering length ($`a=2.75`$ nm) and mass of 23Na atoms to derive the numerical factor. Our traps feature extreme aspect ratios resulting in $`N_{1D}>10^4`$ and $`N_{2D}>10^5`$ while for most standard BEC traps the numbers are significantly smaller.

For a 1D condensate the condition $`\xi =l_t`$ yields a linear density $`\stackrel{~}{n}_{1D}1/4a`$, implying that the linear density of a 1D condensate is limited to less than one atom per scattering length independent of the radial confinement. Therefore, tight transverse confinement, as may be achievable in small magnetic waveguides  or hollow laser beam guides , is by itself not helpful to increase the number of atoms in a 1D condensate. Large 1D numbers may only be achieved at the expense of longer condensates or if the scattering length is smaller.

In anisotropic traps, a primary indicator of crossing the transition temperature for Bose-Einstein condensation is a sudden change of the aspect ratio of the ballistically expanding cloud, and an abrupt change in its energy. The transition to lower dimensions is a smooth cross-over, but has similar indicators. In the 3D Thomas-Fermi limit the degree of anisotropy of a BEC is independent of the number $`N`$ of atoms, whereas in 1D and 2D, the aspect ratio depends on $`N`$. Similarly, the release energy in 3D depends on $`N`$  while in lower dimensions, it saturates at the zero-point energy of the tightly confining dimension(s), when $`N`$ becomes smaller.

A trapped 3D condensate has a parabolic shape and its radius and half-length are given by $`R_{}=l_{}(15Nal_{}/l_z^2)^{1/5}`$ and $`R_z=l_z(15Nal_z^3/l_{}^4)^{1/5}`$ , resulting in an aspect ratio of $`R_{}/R_z=l_{}^2/l_z^2=\omega _z/\omega _{}`$. When the 2D regime is reached by reducing the atom number, the condensate assumes a Gaussian shape with an rms width $`l_z`$ along the axial direction, but retains the parabolic shape radially. The radius of a trapped 2D condensate decreases with $`N`$ as $`R_{}=(128/\pi )^{1/8}(Nal_{}^4/l_z)^{1/4}`$ . Similarly, the half-length of trapped 1D condensates is $`R_z=(3Nal_z^4/l_{}^2)^{1/3}`$ .

Our experiments in which one- and two-dimensional Bose-Einstein condensates were realized were carried out in two different experimental setups. For the study of condensates in a 2D geometry, condensates of $`10^7`$ atoms were generated as described in Refs.  and transferred into an optical trap . The optical trapping potential was generated by focusing a 1064 nm laser into a light sheet using cylindrical lenses, with the tight focus in the vertical dimension to provide optimum support against gravity. This resulted in typical trap frequencies of $`\omega _z/2\pi =790`$ Hz, $`\omega _x/2\pi =30`$ Hz and $`\omega _y/2\pi =10`$ Hz for a laser power of $`600`$mW. The transfer from the magnetic trap into the optical trap was accomplished by turning on the trapping light field and turning down the magnetic trapping potential resulting in a transfer efficiency of more than 50%. The depth of the optical potential and the trap frequencies could be easily varied by changing the power of the trapping beam.

To observe the transition from the 3D Thomas-Fermi regime into a 2D situation, we have adjusted the number of condensate atoms between $`2\times 10^6`$ and $`3\times 10^4`$ by exposing the optically trapped BEC to a thermal sodium atomic beam. Condensates were detected by suddenly releasing the atoms from the trap and taking absorption images after $`15`$ ms free expansion. The condensates dropped by $`15\mu `$m during the $`100\mu `$s imaging time, which is less than $`10\%`$ of the measured length of our shortest condensates. During expansion, the interaction energy is converted almost exclusively into kinetic energy in the tightly confining vertical direction. Thus, the vertical length of the condensate expands quickly while the horizontal dimensions almost retain their size in the trap. The aspect ratio changes dramatically, and for the chosen time-of-flight the axial dimension is even larger than the radial one. The aspect ratio was determined by fitting the condensate with a parabolic Thomas-Fermi distribution which is exact in the large-number limit. For small numbers the vertical condensate shape approaches a Gaussian, but we also used the parabolic fitting function to avoid any bias. A parabolic fitting function may underestimate the rms width of a Gaussian by at most $`20\%`$.

Figures 1a,b show how the expanded condensate became more elongated for small atom numbers, clear evidence for reaching 2D. In Fig. 1c the aspect ratio of condensates in three different optical traps is shown. For all our trap parameters, the aspect ratio approaches a constant value for large atom numbers, which can be calculated using the results of  for the Thomas-Fermi limit. The increase of the aspect ratio for small atom numbers is due to clamping of the vertical length of the condensate because of saturation of the release energy while the width shrinks further. For the weakest trap, using Eq. 2, $`N_{2D}=2.9\times 10^5`$ , while we could observe condensates with as low as $`N_{2D}/10`$.

The saturation of the mean release energy per particle at the kinetic part of the zero-point energy of the trap becomes obvious if the half-length of the expanded condensates is plotted versus the radius (see Fig. 2). For a long enough time-of-flight, the mean release energy is simply proportional to the square of the measured half-length and is given by $`E_{rel}=mR_z(t)^2/14t^2`$. In all our traps the half-length appears to saturate at a value which corresponds to a release energy close to $`\mathrm{}\omega _z/4`$ which is the vertical kinetic zero-point energy.

The 1D experiments were carried out in a Ioffe-Pritchard type magnetic trap with radial and axial trapping frequencies of $`\omega _{}/2\pi =360`$ Hz and $`\omega _z/2\pi =3.5`$ Hz . We obtained an extreme aspect ratio of $`100`$ by reducing the axial confinement during the final evaporation stage. As in the 2D case, the number of atoms in the condensate was lowered by exposing the gas to a thermal sodium beam, followed by a reequilibration time of $`15`$ s. A radio-frequency shield  limited the trap depth to $`2040`$ kHz ($`12\mu `$K). We analyzed the cloud using absorption imaging along one of the radial directions after a ballistic expansion of $`t=4`$ ms. In contrast to the 2D experiments, the aspect ratio of the cloud was not yet inverted after this short time-of-flight. The measured condensate sizes were corrected for the finite imaging resolution of $`5\mu m`$, a correction of less than 10%.

Similar to the 2D experiment, the cross-over to the 1D regime was observed by a change of the aspect ratio when the number of atoms was reduced (Fig.3). In the 3D limit, neglecting the initial radial size and the axial expansion (both $`<1\%`$ corrections) the aspect ratio equals $`\omega _zt`$ independent of $`N`$. The deviation from this behavior below $`5\times 10^4`$ atoms demonstrates the cross-over to 1D behavior. At the same time, the release energy saturated at $`\mathrm{}\omega _{}/2`$, the zero-point kinetic energy of the trapping potential (Fig. 3b). For this trap, Eq. 1 yields $`N_{1D}=1.6\times 10^4`$, while we could observe condensates with as low as $`N_{1D}/2`$. In the 1D geometry, the aspect ratio deviates from the 3D limit for larger ratios of $`N/N_{1D}`$ than in the 2D case, since the interaction energy per particle at the cross-over to 1D is only approximately half the kinetic zero-point energy while at the cross-over to 2D, it is roughly equal to the kinetic zero-point energy.

So far, we have discussed only the condensate and its cross-over from the Thomas-Fermi regime into a lower-dimensional situation. Here, we will briefly address the thermal component and finite temperature effects. The finite trap depth $`U_{\mathrm{trap}}`$ provides constant evaporative cooling which counteracts any residual heating and stabilizes the temperature. The equilibrium temperature in both the 1D and 2D experiment can be estimated to be a constant fraction $`1/\eta `$ of the trap depth $`U_{\mathrm{trap}}`$. For a quantum saturated thermal cloud ($`T<T_c`$), the number of thermal atoms $`N_{\mathrm{th}}`$ can be approximated by simply counting the number of states with an energy below $`k_BT`$, which results in $`N_{\mathrm{th}}(U_{\mathrm{trap}}/\eta \mathrm{})^3/\omega _{}^2\omega _z`$. This estimate assumes that the thermal cloud is still three-dimensional ($`k_BT>\mathrm{}\omega _{,z}`$), in agreement with the situation in the experiment. To be able to discern the condensate from the thermal cloud, $`N_{\mathrm{th}}`$ should not be much larger than $`N_{1D}`$ ($`N_{2D}`$). This simple argument implies that for our 1D trap where $`N_{1D}1.6\times 10^4`$, the maximum allowed trap depth would be $`60`$ kHz assuming a typical $`\eta =10`$ and a minimum condensate fraction of 10%. This is in fair agreement with our experimental observations.

In a magnetic trap, the trap depth can be adjusted independently of the trap frequencies using an rf shield. In an optical trap created using a single Gaussian focus, the trap frequencies are proportional to the square root of the trap depth. Thus, tighter optical traps can store more thermal atoms, yet Eq. 2 implies that $`N_{2D}`$ is lower for tighter traps. Therefore, tight single-focus optical traps are less suitable for the observation of lower-dimensional condensates. Experimentally, we have observed that for weaker traps we could penetrate further into the 2D regime (see Fig. 1c) than for tighter ones, which is consistent with the considerations above.

In our experiments, the thermal cloud is always three-dimensional, which necessarily requires that the critical temperature $`T_c`$ for Bose condensation is also larger than the energy level spacing of the trap, i.e. $`k_BT_c>k_BT>\mathrm{}\omega _t`$. A new physical regime in which the condensation process could be studied in lower dimensions would be reached if thermal excitations freeze out before a BEC forms. This requires that the total number of atoms $`N`$ be smaller than the number of states with an energy smaller than $`\mathrm{}\omega _t`$. Thus, in 1D, the number of atoms may not exceed the aspect ratio of the trap, i.e. $`N<A=\omega _t/\omega _w`$, where $`\omega _w`$ is the trapping frequency in the weakly confining direction, while in 2D the relevant criterion is $`N<A^2`$. For the traps used in our experiments, this implies $`N<100`$ (1D) or $`N<2500`$ (2D), which, at least for 2D, seems to be within experimental reach. The physics of Bose-condensation in 2D has been discussed in several publications. It is not yet clear under what circumstances one will observe quasi-condensates  or the Kosterlitz-Thouless transition . A full understanding of the observation of 2D quantum degeneracy of spin-polarized hydrogen  is still lacking, and controlled experiments with dilute gases could give useful insights. In a 1D geometry a related effect that could be observed is a two-step condensation as discussed in .

Lower-dimensional condensates, as prepared in our experiments, offer many opportunities for further scientific studies. Topological excitations such as solitons (in 1D) and vortices (in 2D) should be much more stable than in 3D, where solitons suffer from kink instabilities and vortices can bend. The character and spectrum of the collective excitations is expected to exhibit a qualtitative change in lower dimensions .

Another area of significant theoretical interest is the study of phase fluctuations  and its relation to the formation of quasi-condensates, which locally behave like ordinary condensates but do not have a globally uniform phase. In 3D, the energy associated with such phase fluctuations is usually higher than $`k_BT_c`$ (except for very extreme aspect ratios), whereas in 1D and 2D it can be lower. It might be possible to observe the phase fluctuations by observing a broadening of the Doppler spectrum of the condensate .

An even more ambitious goal is the observation of a Tonks gas in a one-dimensional geometry . At zero temperature, such a gas of “impenetrable bosons” is realized when the axial distance $`1/\stackrel{~}{n}`$ between atoms exceeds the 1D healing length, $`\xi =l_{}/(2\stackrel{~}{n}a)^{1/2}`$ , resulting in $`\stackrel{~}{n}_{\mathrm{Tonks}}=2a/l_{}^2`$ as a condition for the linear density. Thus, $`\stackrel{~}{n}_{\mathrm{Tonks}}`$ is $`8a^2/l_{}^2`$ times smaller than $`\stackrel{~}{n}_{1D}`$. In 2D, the collision physics is severely altered only for $`a/R_z>1`$ . Such regimes require much tighter confinement than in our experiment and may be realized using optical lattices or magnetic microtraps, or alternatively a larger scattering length, for example near a Feshbach resonance.

In conclusion, we have prepared lower-dimensional condensates in optical and magnetic traps. The cross-over into lower-dimensional behavior was indicated by a change in the aspect ratio of the cloud and a saturation of the release energy as the condensate number was lowered. Due to the extreme geometries of our traps the number of atoms at the cross-over to lower-dimesionality is rather large ($`>10^5`$ in the 2D case) which provides a good starting point for the exploration of phenomena which only occur in one or two dimensions.

This research is supported by NSF, ONR, ARO, NASA, and the David and Lucile Packard Foundation. A. E. L. and A. P. C. acknowledge additional support by a fellowship from NSF and JSEP, respectively.