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# Final state interaction in spin asymmetry and GDH sum rule for incoherent pion production on the deuteron

## 1 Introduction

The spin response or vector target asymmetry of the total photo absorption cross section of a hadron or nucleus has come into focus Dre95 ; Proc01  with recent interest in the Gerasimov-Drell-Hearn (GDH) sum rule Ger65 ; DrH66 . This sum rule connects the anomalous magnetic moment $`\kappa `$ of a particle of mass $`M`$, charge $`eQ`$, and spin $`S`$ with the energy weighted integral over the difference $`\sigma ^P(k)\sigma ^A(k)`$ of the total photoabsorption cross sections for circularly polarized photons on a target with spin parallel and antiparallel to the spin of the photon

$$I^{GDH}(\mathrm{})=_0^{\mathrm{}}\frac{dk}{k}\left(\sigma ^P(k)\sigma ^A(k)\right)=4\pi ^2\kappa ^2\frac{e^2}{M^2}S.$$
(1)
Here the anomalous magnetic moment is defined by the total magnetic moment operator of the particle $`\stackrel{}{M}=e(Q+\kappa )\stackrel{}{S}/M`$, where $`\stackrel{}{S}`$ denotes the spin operator of the target.

For the deuteron, one finds a very small anomalous magnetic moment $`\kappa _d=0.143`$ resulting in a GDH prediction of $`I_d^{GDH}=0.65\mu `$b, which is more than two orders of magnitude smaller than the nucleon values, i.e., $`I_p^{GDH}=204.8\mu `$b for the proton and $`I_n^{GDH}=233.2\mu `$b for the neutron. The explicit evaluation of the spin asymmetry for various reaction channels, essentially photodisintegration and coherent and incoherent single pion production, has shown, that this small GDH sum rule value is the result of large cancellations between the contributions of the individual channels ArK97 . For photodisintegration alone one finds a large negative spin asymmetry close to the break-up threshold which arises from the large isovector $`M1`$-transition to the resonant $`{}_{}{}^{1}S_{0}^{}`$-state. In fact, the explicit evaluation of the GDH integral for photodisintegration up to an energy of 550 MeV yields a large negative contribution of $`I_{\gamma dnp}^{GDH}(550\text{MeV})=413\mu `$b, which almost equals the sum of the GDH values of proton and neutron. We would like to remark that for this channel relativistic contributions were quite sizeable already at rather low energies below 50 MeV, reducing the GDH integral from $`665\mu `$b by about one third to the foregoing value. Furthermore, the GDH integral had already reached convergence at 550 MeV. In view of this negative contribution a corresponding positive contribution has to be expected from the other channels, i.e., mainly from pion photoproduction.

In this context it has been suggested to ‘measure’ in the absence of neutron targets the neutron spin asymmetry by measuring the spin asymmetry of the deuteron for the pion photoproduction channels using a vector polarized deuteron target, thus allowing the explicit evaluation of the GDH integral for the neutron. The implicit tacit assumption underlying this suggestion is that the contributions of pion production on proton and neutron in the deuteron add up incoherently. As was shown in ArK97 , already for the impulse approximation this is not the case. With the present note we will demonstrate that it is even less fulfilled if final state interaction effects are included.

Notwithstanding the ‘caveats’ of such an ‘extraction‘ Are00 , it is certainly of interest to study the deuteron spin asymmetry for the pion production channels, because in general polarization observables will give additional valuable information for checking the spin degrees of freedom of the elementary pion production amplitude of the neutron, provided, and this is very important, that one has under control all interfering interaction effects which prevent a simple extraction of this amplitude.

## 2 Final state interaction in incoherent pion production on the deuteron

In our previous evaluation ArK97 , the incoherent pion production contribution to spin asymmetry and GDH integral had been evaluated in the pure impulse approximation (IA) only, i.e., neglecting any final state interaction effects (FSI) and possible two-body contributions to the production operator. In this framework, the reaction proceeds via the pion production on one nucleon while the other nucleon acts merely as a spectator. In view of the dominance of the quasifree production process one could expect that the IA would work reasonably well for charged pion production. However, for neutral pion production there is some double counting with respect to the coherent process due to the neglect of $`NN`$-rescattering in the final state with the effect that the final state is not orthogonal to the $`{}_{}{}^{3}S_{1}^{}`$-$`{}_{}{}^{3}D_{1}^{}`$ state of the deuteron. Thus in this case one expects a sizeable overestimation by the IA, because it contains a fraction of the coherent channel. This has been confirmed in LeS00 ; DaA03  where FSI effects were considered, and a sizeable reduction of the unpolarized total and differential cross sections of the incoherent neutral pion production had been found due to the above mentioned non-orthogonality, whereas for charged pion production the FSI effects were significantly smaller.

In DaA03  we have included besides the pure impulse approximation the complete rescattering by the final state interaction within each of the two-body subsystems $`NN`$\- and $`\pi N`$. For the pion the rescattering refers to the scattering on the spectator nucleon because the rescattering on the active nucleon is already included in the dominant elementary $`M_{1+}^{3/2}`$ multipole. Therefore, the total transition matrix element reads in this approximation

$`^{(t\mu )}`$ $`=`$ $`^{(t\mu )IA}+^{(t\mu )NN}+^{(t\mu )\pi N}`$ (2)
in an obvious notation. A graphical representation of the scattering matrix is shown in Fig. 1. The necessary half-off-shell two-body scattering matrices were obtained from separable representations of realistic $`NN`$\- and $`\pi N`$-interactions which gave good descriptions of the corresponding phase shifts Dar02 . For $`NN`$-rescattering, we have included all partial waves with total angular momentum $`J3`$ and for $`\pi N`$-rescattering $`S`$\- through $`D`$-waves. As $`NN`$-interaction we have used the Paris potential, but we have also tried the Bonn r-space potential obtaining essentially the same result. For further details with respect to the rescattering contributions we refer to DaA03 .

For the elementary pion photoproduction operator, we have taken as in our previous work the standard pseudovector Born terms and the contribution of the $`\mathrm{\Delta }`$-resonance as described in detail in ScA96 , and a satisfactory description of pion photoproduction on the nucleon in the $`\mathrm{\Delta }`$-resonance region DaA03  was achieved.

The major effect of $`NN`$\- and $`\pi N`$-rescattering in incoherent pion photoproduction on the deuteron was a reduction of the total unpolarized cross section which amounts in the maximum of the $`\mathrm{\Delta }`$(1232)-resonance region for charged pion photoproduction to about 5 percent and to about 35 percent for $`\pi ^0`$-photoproduction. Thus for charged pion production the IA appears to be a reasonable approximation within these five percent, but not for neutral pion production as already mentioned above. The dominant effect of FSI came from $`NN`$-rescattering whereas $`\pi N`$-rescattering was much less important, almost negligible (compare the dashed curves with the solid ones in Fig. 11 of DaA03  which are almost indistinguishable). With respect to experimental data a satisfactory agreement was achieved.

## 3 Results for spin asymmetry and GDH integral

In the meantime, we have evaluated also the spin asymmetry for these reactions. The results are presented in Fig. 2, where the upper part shows the total photoabsorption cross sections $`\sigma ^P`$ for circularly polarized photons on a target with spin parallel to the photon spin, the middle part $`\sigma ^A`$, the one for antiparallel spins of photon and target and the lower part the spin asymmetry $`\sigma ^P\sigma ^A`$ for the individual contributions of the different pion charge states to incoherent pion photoproduction on the deuteron. For comparison, we also show in the same figure the results on the free nucleon by the dash-dotted curves. In the case of $`\pi ^0`$ it is the sum of the proton and neutron asymmetries.

One notes for the cross sections $`\sigma ^P`$ and $`\sigma ^A`$ as well as for the spin asymmetry of the nucleons and the deuteron qualitatively a similar behaviour, although for the deuteron the maxima and minima are smaller and also slightly shifted towards higher energies. Furthermore, in $`\sigma ^P`$ the charged pion contributions show a larger deviation between the IA and the elementary one, whereas for $`\sigma ^A`$ the differences are smaller. In contrast to this, one notes for the neutral pion contributions a much closer behaviour between the IA and the elementary reaction for both cross sections and the difference.

FSI effects appear for charged pion production mainly in $`\sigma ^P`$ while for neutral pions they are of equal importance for both $`\sigma ^P`$ and $`\sigma ^A`$, again because of the non-orthogonal final state in IA. The bottom panels in Fig. 2 show that final state interactions lead to an overall strong reduction of the spin asymmetry in the energy region of the $`\mathrm{\Delta }`$(1232)-resonance. This reduction becomes about 170 $`\mu `$b for $`\pi ^0`$-production and about 35 $`\mu `$b for charged pions on the $`\mathrm{\Delta }`$-peak. Thus even for charged pion production the IA is not anymore a reasonable approximation as it was for the unpolarized total cross section. Moreover, already the IA deviates significantly from the corresponding nucleon quantities for charged pion production. These facts underline our doubts concerning an ’extraction’ of the neutron spin asymmetry from the one of the deuteron. It is also obvious that $`\sigma ^P`$ is much larger than $`\sigma ^A`$ because of the $`\mathrm{\Delta }`$-excitation, in particular in the case of $`\pi ^0`$-production. The influence of FSI stems predominantly from $`NN`$-rescattering whereas $`\pi N`$-rescattering is much smaller. In fact, the dashed curves, representing the inclusion of $`NN`$-FSI alone, and the solid ones with both $`NN`$\- and $`\pi N`$-FSI appear almost indistinguishable. It is interesting to note that the size of the reduction of $`\sigma ^P\sigma ^A`$ in the IA by FSI for $`\pi ^0`$-production (about 170 $`\mu `$b in the maximum), related to the already mentioned non-orthogonality effect, is comparable in magnitude, though somewhat larger, to the coherent contribution to the spin asymmetry of 120 $`\mu `$b in the maximum as reported in ArK97 .

In Fig. 3 the corresponding GDH integrals are shown for the separate channels and in Fig. 4 for the sum of all three pion channels as function of the upper integration limit. One notes again the significant reduction by FSI, mainly through $`NN`$-rescattering, but the $`\pi N`$-rescattering effect is now distinguishable although still quite small (compare the dashed with the solid curves in Figs. 3 and 4).

The values of the GDH integral up to 550 MeV for all three channels and their sum are listed in Table 1. A sizeable positive contribution comes from $`\pi ^0`$-production whereas the charged pions give a negative but - in absolute size - smaller contribution to the GDH value. The inclusion of $`NN`$-FSI reduces the total GDH integral to one half of the IA value which is then further reduced, but on a much smaller scale by $`\pi N`$-rescattering. Furthermore, we would like to point out that the total value of the integral of 87 $`\mu `$b is thus considerably smaller than the sum of the neutron and proton values for the present model of the elementary model, namely $`I_n^{GDH}(550\text{MeV})+I_p^{GDH}(550\text{MeV})=197\mu `$b. This underlines our caveat, that a simple extraction of the neutron spin asymmetry from a measurement on the deuteron is not possible.

## 4 Concluding remarks

If one adds the previously reported values of the GDH integral from the photodisintegration channel ($`I_{\gamma dnp}^{GDH}(550\text{MeV})=413\mu `$b) and the coherent pion production ($`I_{\gamma d\pi ^0d}^{GDH}(550\text{MeV})=63\mu `$b) from ArK97 , one finds for the total GDH value from explicit integration up to 550 MeV a negative value $`I_d^{GDH}(550\text{MeV})=263\mu `$b which has to be compared to the value $`I_d^{GDH}(\mathrm{})=0.65\mu `$b. However, as was already mentioned in ArK97 , the model of the elementary production amplitude above the $`\mathrm{\Delta }`$-resonance is not very realistic, because it had been constructed primarily to give a realistic description of the $`\mathrm{\Delta }`$-resonance region and not at higher energies. In fact, it grossly underestimates the GDH integral up to 550 MeV if we compare $`I_{n+p}^{GDH}(550\text{MeV})=197\mu `$b of our model with the most recent MAID 2000 analysis Maid  yielding a value $`I_{n+p}^{GDH}(550\text{MeV})=282\mu `$b. The latter value is based on a multipole analysis of experimental pion photoproduction data. Thus it is clear that the large negative value for the deuteron will be reduced significantly using an elementary production operator which yields a better description above the $`\mathrm{\Delta }`$-resonance. Moreover, the pion production contribution has not yet reached convergence at 550 MeV (see Figs. 3 and 4). In fact, one expects at energies above 550 MeV further positive contributions from pion production Tia02 . Thus for a more quantitative evaluation one has to use a more realistic elementary operator. In addition, an appropriate $`NN`$-interaction model which includes retardation effects and inelasticities is needed as well as the consideration of relativistic effects which turned out to be very important for the spin asymmetry of the photodisintegration channel ArK97  as mentioned above. In addition, a genuine three-body approach would be desirable.

Thus we would like to conclude that, notwithstanding the shortcomings of the present work, the results clearly show first of all the importance of final state interaction effects in the spin asymmetry of the deuteron, a feature which certainly will remain true in a more realistic treatment of the energy region above the $`\mathrm{\Delta }`$-resonance. Secondly, it is obvious that a measurement on the deuteron will not provide direct access to the spin asymmetry of the neutron. However, the deuteron spin asymmetry will certainly provide us with an important check observable for testing our knowledge of the pion photoproduction on the neutron and thus will give us valuable information on the neutron’s spin asymmetry in an indirect manner if one has a reliable model for the FSI and possible other two-body effects at hand for the analysis.

## Acknowledgement

This work was supported by the Deutsche Forschungsgemeinschaft (SFB 443). E.M. Darwish acknowledges a fellowship from Deutscher Akademischer Austauschdienst (DAAD).


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# Octahedral Tilting in 𝐀𝐂𝐮_𝟑𝐑𝐮_𝟒𝐎_𝟏𝟐 (A=Na,Ca,Sr,La,Nd)

## 1 Introduction

Despite its striking simplicity the perovskite structure, $`\mathrm{ABX}_3`$, contains numerous crystallographic variations giving room for a huge class of compounds . Among these the vast majority comprises oxides and fluorides , but also chlorides, hydrides, oxynitrides, and sulfides. The great interest in these materials is motivated by a variety of exciting dielectric, magnetic, electrical, optical, and catalytic properties, with several technological applications.
For optimal tailoring of materials much work on the perovskite-related compounds concentrates on the interrelations between deviations from the ideal perovskite structure and physical properties. These crystallographic deviations can be grouped into three different mechanisms : While distortions of the characteristic $`\mathrm{BX}_6`$ octahedra and cation displacements within the octahedra are mainly driven by electronic instabilities of the octahedral metal ion, octahedral tiltings represent the most common deviation and are observed when the A cation is too small for filling the space between regularly ordered octahedra. In this situation, octahedral tilting represents the lowest energy distortion, since it allows to adjust the A–O distances while leaving the first coordination sphere of the M cation intact, and changing mainly the soft M–O–M bond angle rather than the M–O bond length.
Of particular interest in this context are the perovskite-like compounds of the kind $`\mathrm{AA}_3^{}\mathrm{B}_4\mathrm{O}_{12}`$, where the B–O–B bond angle is the relevant quantity in order to optimize both the $`\mathrm{A}`$–O and $`\mathrm{A}^{}`$–O bond lengths. Studying these materials thus promises deeper insight into the mechanisms driving the octahedral tilting. In addition, this material class shows extraordinary physical properties. While $`\mathrm{CaCu}_3\mathrm{Mn}_4\mathrm{O}_{12}`$ is a ferromagnetic semiconductor with high Curie temperature and large magnetoresistance , $`\mathrm{CaCu}_3\mathrm{Ti}_4\mathrm{O}_{12}`$ is known for its unusually high low-frequency dielectric constants . In contrast, the metallic ruthenates of the type $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ (A=Na,Ca,La) are Pauli paramagnets  and display valence degeneracy . The crystal structures of the latter class have been studied recently by EXAFS and XRD, revealing considerable deviations of the measured interatomic distances from those expected from a bond valence approach .
The present study investigates the relationship between the octahedral tiltings and the electronic properties of the ruthenates $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ (A=Na,Ca,Sr,La,Nd). The discussion is based on electronic structure calculations within density functional theory, which are known for their predictive power (see e.g. Refs.  and references therein). As a result, the specific bond lengths as well as the discrepancies between the experimental interatomic distances of the class $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ and those proposed by the bond valance approach can be understood from the electronic properties and the type of chemical bonding.

## 2 Crystal Structure

The compounds of the class $`\mathrm{AA}_3^{}\mathrm{B}_4\mathrm{O}_{12}`$ crystallize in a body-centered cubic $`2\times 2\times 2`$ superstructure of the simple cubic perovskite structure with space group $`Im\overline{3}`$ (No. 204). The atoms are located at the following Wyckoff positions: A ($`2a`$) at (0,0,0), $`\mathrm{A}^{}`$ ($`6b`$) at $`(\frac{1}{2},0,0)`$, B ($`8c`$) at $`(\frac{1}{4},\frac{1}{4},\frac{1}{4})`$, and O ($`24g`$) at $`(x,y,0)`$. The crystal structure is shown in Fig. 1,

where the $`\mathrm{BO}_6`$ octahedra are easily identified. The tilting of the octahedra is controlled by the oxygen position, which, for all the ruthenates under study, is specified by $`x_\mathrm{O}0.175`$ and $`y_\mathrm{O}0.305`$. The deviation from the ideal values $`x_\mathrm{O}=y_\mathrm{O}=0.25`$ causes a rotation of the octahedra around the  axis. As a consequence, the A sites are partitioned into the A site at (0,0,0) and the $`\mathrm{A}^{}`$ site, which takes three quarters of the original A positions. In particular, the $`\mathrm{A}^{}`$ sites are strongly affected by the oxygen atom shifts away from the ideal position and thus their surrounding experiences the largest distortion. As a consequence, three different $`\mathrm{A}^{}`$–O distances of $``$ 2.0 Å, 2.8 Å, and 3.2 Å appear, each forming an approximately square-planar coordination and thus providing an ideal geometry for a Jahn-Teller active ion as e.g. $`\mathrm{Cu}^{2+}`$ . The $`\mathrm{CuO}_4`$ squares can be easily identified in Fig. 1.
For the ruthenates $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ (A=Na,Ca,Sr,La,Nd) studied in the present work, crystallographic data were determined by Ebbinghaus et al. . The lattice constants are similar to those reported by Labeau et al.  as well as Subramanian and Sleight . Both the lattice constants and oxygen parameters of these compounds show only slight deviations and amount to $`a7.4`$ Å as well as $`x_\mathrm{O}0.175`$ and $`y_\mathrm{O}0.305`$ as mentioned above.

## 3 Method of Calculation

The electronic structure calculations were performed within the framework of density functional theory and the local density approximation using the augmented spherical wave (ASW) method . In order to represent the correct shape of the crystal potential in the large voids, additional augmentation spheres were inserted into the open crystal structures. Optimal augmentation sphere positions as well as radii of all spheres were found automatically by the sphere geometry optimization (SGO) algorithm . The basis sets comprised Cu $`4s`$, $`4p`$, $`3d`$, Ru $`5s`$, $`5p`$, $`4d`$, $`4f`$, and O $`2s`$, $`2p`$ as well as states of the additional augmentation spheres. In addition, Na $`3s`$, $`3p`$, $`3d`$; Ca $`4s`$, $`4p`$, $`3d`$, $`4f`$; Sr $`5s`$, $`5p`$, $`4d`$, $`4f`$; La/Nd $`6s`$, $`6p`$, $`5d`$, $`4f`$ states were used for the A cation. The Brillouin zone sampling was done using an increasing number of $`𝐤`$ points within the irreducible wedge ranging from 17 to 1255 points to ensure convergence of the results with respect to the $`𝐤`$-space grid. In addition to the analysis of the (partial) densities of states we will also address the question of chemical bonding in terms of the covalent bond energy, which was recently proposed  as an extension to the concept of the crystal orbital overlap population (COOP) . In short, the covalent bond energy covers those contributions to the total energy of a crystal, which arise from the hybridization of orbitals located at different atoms.

## 4 Results and Discussion

Partial densities of states (DOS) for all five compounds under consideration are displayed in Fig. 2.

The electronic structure in the energy window shown is dominated by Cu $`3d`$, Ru $`4d`$, and O $`2p`$ states. In addition, Nd $`4f`$ states cause a sharp peak at and slightly above $`\mathrm{E}_\mathrm{F}`$ for $`\mathrm{NdCu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$. The gross features are very similar for all compounds. Three energy ranges can be distinguished. In the broad interval from about -8 to -3 eV oxygen $`2p`$ states dominate but are complemented by considerable contributions from the transition metal $`d`$ states due to covalent bonding. Whereas in the energy range from -3 to -2 eV a sharp Cu $`3d`$ peak appears, electronic states between -2 and 0.5 eV, and hence metallic conductivity, derive mainly from broader Ru $`4d`$ bands. Covalent type bonding leads to finite oxygen $`2p`$ contributions above -3 eV. This is confirmed by covalent bond energy curves calculated for the sodium compound as shown in Fig. 3.

Both the $`\mathrm{Cu}`$$`\mathrm{O}`$ and the $`\mathrm{Ru}`$$`\mathrm{O}`$ curves are negative and positive at energies below and above -3 eV, respectively, indicative of bonding and antibonding states in the energy regions, where the O $`2p`$ and the transition metal $`d`$ states dominate. However, due to the higher $`d`$ electron count of Cu as compared to Ru, the $`\mathrm{Cu}`$$`\mathrm{O}`$ antibonding states are filled, leading to a vanishing contribution of these bonds to the chemical stability. In contrast, the integrated $`\mathrm{Ru}`$$`\mathrm{O}`$ covalent bond energy curve at $`\mathrm{E}_\mathrm{F}`$ has a finite value indicative of the stabilizing net contribution of this bond. Finally, metal-metal bonding results in small peaks between -3 and -2 eV and above the Fermi energy.
All states which are not displayed in Fig. 2 play only a very small role in the energy interval shown. In particular, apart from the Nd $`4f`$ states, the A cation electrons do not contribute to the covalent-type bonding but are distributed over the solid. As a consequence, changes at the A cation site show up mainly in the modified total electron count.
Ebbinghaus et al.  related the measured atomic distances for $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ (A=Na,Ca,Sr,La,Nd) to the predictions of the bond valence model. The latter is an empirical model, which connects the valences and the mutal distances of the atoms . It starts out from ionic configurations but looses accuracy in covalently bonded crystals. For the divalent A cations the Ru-O distances were found to agree with the expected values. In the case of A=Na the bond length is longer, while for A=La,Nd it is shorter than predicted by the bond valence model.
In order to understand the influence of octahedral tilting on the electronic properties and to analyze the mentioned discrepancies reported by Ebbinghaus et al. we performed additional calculations using hypothetical crystal structures. In these setups the oxygen atoms were shifted away from the measured positions to the ideal position $`x_\mathrm{O}=0.25`$, $`y_\mathrm{O}=0.25`$ and to $`x_\mathrm{O}=0.15`$, $`y_\mathrm{O}=0.35`$. These positions correspond to zero tilting of the octahedra and to an exaggerated tilting, respectively. Note that shifting the oxygen position mainly affects the Cu–O bond lengths, while the effect for the Ru–O and A–O distances is of second order. The partial DOS for the hypothetical structures of $`\mathrm{NaCu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ are displayed in Fig. 4.

Considerable changes as compared to the results for the experimental crystal structure (see Fig. 2) are observed. Turning to the ideal structure first, we observe (i) a considerable broadening of the O $`2p`$ dominated states and (ii) a striking sharpening of the Cu $`3d`$ states. Both effects are readily understood from the oxygen shifts. The latter cause an increase of the Cu–O distances and, to a lesser degree, a decrease of the Ru–O distances, leading to a slightly larger $`2p`$$`4d`$ overlap. As a consequence, larger Ru $`4d`$ contributions at energies below -3 eV are observed, whereas the Cu $`3d`$ fraction is almost negligible in this region. At the same time, Ru $`4d`$ and O $`2p`$ admixture to the sharp Cu $`3d`$ peak is likewise very small. To sum up, shifting the oxygen atoms to their ideal positions leads to an effective decoupling of the compound into $`\mathrm{RuO}_6`$ octahedra and Cu atoms, which are effectively separated and thus do no longer form a stable solid.
On the contrary, for the hypothetical structure with the oxygen shift away from the ideal position exaggerated (i) the oxygen states have moved to lower energies and (ii) the Cu $`3d`$ states do no longer form a distinct peak but have attained a rather itinerant character. The latter goes along with an increased similarity of the Cu $`3d`$ and O $`2p`$ partial DOS. The increased covalent type bonding between these two states is also reflected by large contributions to the covalent bond energy (not shown), negative below -4 eV and positive above, leading to a net antibonding integral at $`\mathrm{E}_\mathrm{F}`$. The increased $`2p`$$`3d`$ bonding is in contrast to a slight decrease of the bonding between the Ru $`4d`$ and O $`2p`$ states due to the larger extension of the $`\mathrm{RuO}_6`$ octahedra. Thus the hypothetical structure with exaggerated oxygen shifts likewise suffers from an increase of antibonding at the expense of bonding states.
Together with the instability of the hypothetical structure with ideal oxygen positions we conclude that the experimental structure is due to an optimal balance of different types of bonds, namely $`2p`$$`3d`$ and $`2p`$$`4d`$. This balance is less affected by the A cations, which do not take part in covalent bonding but have lost their outer electrons. For this reason, from the point of view of chemical bonding, there is no means to optimize the A–O bond length. Moreover, as for the Ru–O distance, the A–O distance is only to a small degree affected by the tilting. Finally, the different types of bonding present in these compounds give an additional explanation for the deviations of the experimental interatomic distances from those expected from the bond valence model.

## 5 Conclusions

The electronic properties of the perovskite-like ruthenates $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$ are governed by strong covalent bonding between the transition metal $`d`$ and the oxygen $`2p`$ electrons. While Ru–O bonds via the corresponding bond-lengths influence mainly the size of the octahedra and hence the lattice constant, the octahedral tilting is to a large part due to the Cu–O bonding.
As compared to the ideal perovskite structure the tilting of the characteristic $`\mathrm{RuO}_6`$ octahedra has only little effect on the Ru–O bonding. In contrast, the Cu–O distances undergo serious changes, leading eventually to the square-planar coordination of copper. Finally, the unusual A–O distances and the failure of the bond valence approach are due to the fact that their response to the tilting is only small and the structure does not offer any possibility to simultaneously optimize the A–O and the Cu–O bond lengths.
In conclusion, octahedral tilting as discussed for $`\mathrm{ACu}_3\mathrm{Ru}_4\mathrm{O}_{12}`$, arises from the interplay of covalent bonding between different atomic species, leading to optimized bond lengths between all atoms involved. This general principle is of rather universal nature and applies to a large variety of compounds.

## Acknowledgements

Fruitful discussions with S. G. Ebbinghaus and A. Weidenkaff are gratefully acknowledged. This work was supported by the Deutsche Forschungsgemeinschaft through SFB 484.


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# Scaling function for self-avoiding polygons

## 1 Introduction

The model of self-avoiding polygons (SAPs) is an important unsolved combinatorial problem in statistical mechanics . In this article, we consider the model of SAPs in two dimensions. SAPs counted by perimeter are the canonical model of ring polymers, while when also counted by area, they serve as a model of vesicles . The model also has connections with many other models of statistical mechanics where boundaries of certain cluster types play a role, notably in percolation and in spin models such as the Ising model and the Potts model, see also . Despite its importance, there are only a few known rigorous results about SAPs, almost all information arising from numerical investigations . Promising new developments however arise from the theory of stochastic processes , see also  (this volume). Recently, we verified numerically a conjecture of one of us about the scaling function for SAPs, which describes the singular part of the SAP perimeter and area generating function about its tricritical point . The prediction of the scaling function also gives the distribution of area moments. The conjecture was already stated in 1995 , as a result of a systematic investigation of simple exactly solvable subclasses of SAPs. There it was noticed that the critical exponents of rooted SAPs coincide with the exponents of staircase polygons, where the scaling function had been computed . This led to the question whether both scaling functions are of the same type.

Over the years, it turned out that the mathematical structure underlying exact solvability is given by $`q`$-algebraic functional equations. They arise from the requirement that the polygon model is built up recursively, see e.g. . This general type of functional equation appears first, within the framework of algebraic languages, in , together with the discussion of the area distribution for simple polygon models showing a square-root singularity. However, the article  does not contain a derivation of its central result. Recently, we investigated the scaling behaviour of general $`q`$-algebraic functional equations . The techniques used for handling $`q`$-algebraic functional equations are applicable in a wide variety of problems, see e.g.  for exact low order cluster moments of asymmetric compact directed percolation. An important outcome of our previous analysis was that the scaling behaviour generically depends only on the singularity of the perimeter generating function. This remarkable kind of universality further supported the above conjecture and led us to test it numerically.

Very recently, investigations on the self-avoiding walk problem using the theory of stochastic processes led to a number of predictions of the behaviour of SAPs in the scaling limit. One of them is that the scaling limit of the half plane infinite SAP is the outer boundary of the union of two Brownian excursions from $`0`$ to $`\mathrm{}`$ in the upper half plane . Since the area under a Brownian excursion is Airy distributed , this would suggest that the area moments of SAPs obey an Airy type distribution. This is consistent with our conjecture that the SAP scaling function is the logarithm of an Airy function and also illuminates the connection with the model of staircase polygons, whose scaling limit is described by Brownian excursions.

In the remainder of this article we first introduce polygon models, in particular self-avoiding polygons, and discuss their critical behaviour. We then consider $`q`$-algebraic functional equations and show how to extract scaling behaviour in the vicinity of a square-root singularity from the functional equation. The following section analyses the exactly solvable example of bar-graph polygons, using the techniques described in the previous section. The next section on self-avoiding polygons contains a summary of the analysis of recently obtained exact enumeration data for polygons on the square lattice to perimeter 100, the hexagonal lattice to perimeter 140 and the triangular lattice to perimeter 58. The analysis confirms the conjectured form of the scaling function in that predicted exact amplitude combinations are confirmed to within a numerical accuracy of 5–6 significant digits. This section also explains the Monte-Carlo simulation method, which we performed on the square lattice for polygons up to perimeter 2048, and confirms the conjectured form of the scaling function within a numerical accuracy of 3 significant digits. A concluding section discusses possible applications of our results and methods.

## 2 Polygon models and their scaling behaviour

For concreteness, we discuss models of polygons defined on the square lattice $`^2`$. These models can be defined similarly for other lattices as well as in the continuous case. A self-avoiding polygon (SAP) is a closed, non-intersecting loop on the edges of the square lattice. Important subclasses are staircase polygons and bar-graph polygons , whose obvious definition may be extracted from Figure 1.

Whereas the latter two models have been solved exactly, as also discussed below, for SAPs there are very few rigorous results, complemented by a number of numerical investigations. Let $`p_{m,n}`$ denote the number of different polygons of perimeter $`m`$ and area $`n`$, respectively, where we regard translated polygons as equal. The object of interest is the perimeter and area generating function

$$G(x,q)=\underset{m,n}{}p_{m,n}x^mq^n,$$
(2.1)
where we introduced a perimeter activity $`x`$ and an area activity $`q`$. Sometimes, horizontal and vertical perimeter are distinguished, leading to an anisotropic perimeter and area generating function $`G(x,y,q)`$. The function $`G(x,1)`$ is called perimeter generating function. Of particular interest is the singular behaviour of $`G(x,q)`$ as a function of $`x`$ and $`q`$, which translates to the behaviour of the coefficients $`p_{m,n}`$ in the limit of large perimeter and area.

The above models display a so-called collapse transition between a phase of extended and a phase of deflated polygons : in the extended phase $`q=1`$, the mean area of polygons $`a_m`$ of perimeter $`m`$ grows asymptotically like $`m^{3/2}`$, whereas it grows like $`m`$ in the deflated phase $`q<1`$. It can be shown that in the limit $`q0`$ the generating function is dominated by polygons of minimal area. Since for SAPs these polygons may be viewed as branched polymers, the phase $`q<1`$ is also referred to as the branched polymer phase. This change of asymptotic behaviour is reflected in the singular behaviour of the perimeter and area generating function. Typically, the line $`q=1`$ is a line of finite essential singularities for $`x<x_c`$. The line $`x_c(q)`$, where $`G(x,q)`$ is singular for $`q<1`$, is typically a line of algebraic (staircase, bar-graph) or logarithmic (SAPs) singularity. For branched polymers in the continuum limit, the logarithmic singularity has been recently proved in  (see also this volume).

Of special interest is the point $`(x_c,1)`$ where these two lines of singularities meet. The behaviour of the singular part of the perimeter and area generating function about $`(x_c,1)`$ is expected to take the special form

$$G(x,q)G^{(reg)}(x,q)+(1q)^\theta F((x_cx)(1q)^\varphi ),(x,q)(x_c^{},1^{}),$$
(2.2)
where $`F(s)`$ is a scaling function of combined argument $`s=(x_cx)(1q)^\varphi `$, commonly assumed to be regular at the origin, and $`\theta `$ and $`\varphi `$ are critical exponents. The singular behaviour about $`q=1`$ at the critical point $`x_c`$ is then given by $`G^{(sing)}(x_c,1)(1q)^\theta F(0)`$. This scaling assumption implies an asymptotic expansion of the scaling function of the form

$$F(s)=\underset{k=0}{\overset{\mathrm{}}{}}\frac{f_k}{s^{(k\theta )/\varphi }}.$$
(2.3)
The leading asymptotic behaviour characterises the singularity of the perimeter generating function via $`G(x,1)f_0(x_cx)^\gamma `$, where $`\theta +\varphi \gamma =0`$. The first singularity of $`F(s)`$ on the negative axis determines the singularity along the curve $`x_c(q)`$. The locus on the axis (say at $`s=s_c`$) determines the line $`x_c(q)x_cs_c(1q)^\varphi `$ near $`q=1`$, which meets the line $`q=1`$ vertically for $`\varphi <1`$.

The area moments $`g_k(x)`$ are defined as coefficients of the (formal) expansion of the generating function about $`q=1`$

$$G(x,q)=\underset{k}{}g_k(x)(1q)^k,g_k(x)=\frac{(1)^k}{k!}\underset{m,n}{}n(n1)\mathrm{}(nk+1)p_{m,n}x^m.$$
(2.4)
Note that $`g_0(x)=G(x,1)`$ is the perimeter generating function. The higher moments $`g_k(x)`$ can be computed recursively using $`g_l(x)`$, where $`l<k`$ using the functional equation . There is an important relation between the scaling function and the area moments: The coefficients $`f_k`$ in the asymptotic expansion of the scaling function are the leading singular amplitudes of the area moments $`g_k(x)`$. This follows from the scaling assumption which implies that the leading singular behaviour of the area moments is of the form

$$g_k^{(sing)}(x)\frac{f_k}{(x_cx)^{\gamma _k}}(xx_c^{}),$$
(2.5)
where $`\gamma _k=(k\theta )/\varphi `$. Thus, information about the scaling function can be obtained from the leading singular behaviour of the area moments which are, in turn, obtainable by a numerical analysis, extrapolating finite-size data.

## 3 $`q`$-Algebraic functional equations

Due to the difficulty of the SAP problem, simple subclasses of SAPs have been analysed in the past; for example rectangles, Ferrers diagrams, stacks, staircase polygons, bar-graph polygons, convex polygons and column-convex polygons, among others . All these models share the special property that they are directed, i.e. they can be thought of as being built up by adding consecutive layers of squares. This results in a special recursion for the coefficients $`p_{m,n}`$ or a specific functional equation for the generating function $`G(x,q)`$. Over the years it has become clear that the underlying structure is a $`q`$-algebraic functional equation of the form

$$P(G(x,q),G(qx,q),\mathrm{},G(q^Nx,q),x,q)=0,$$
(3.1)
where $`P(y_0,y_1,\mathrm{},y_N,x,q)`$ is a polynomial in $`y_0,y_1,\mathrm{},y_N,x`$ and $`q`$. All exactly solved polygon models satisfy such a functional equation (with $`x`$ conjugate to the (horizontal) perimeter and $`q`$ conjugate to the area). For the example of bar-graph polygons, see the next section. No such recursion is known for SAPs, however. The limit $`q1`$ in (3.1) generally leads to an algebraic differential equation, i.e. an algebraic equation in $`x`$, $`G(x,1)`$ and its derivatives. The exactly solved polygon models, however, result in a purely algebraic equation, i.e. in the non-trivial polynomial identity

$$P(G(x,1),G(x,1),\mathrm{},G(x,1),x,1)=0.$$
(3.2)
Not much is known about the singular behaviour of general $`q`$-algebraic functional equations. The $`q`$-linear case, however, has been treated in some detail, see  and references therein. The polygon models of rectangles, Ferrers diagrams, and stacks are $`q`$-linear , whereas the other exactly solved models cited above satisfy $`q`$-quadratic functional equations. Using (3.2), we see that the perimeter generating function $`G(x,1)`$ displays an algebraic singularity at some point $`x_c`$. The most direct way to extract the scaling function about $`x=x_c`$ and $`q=1`$, whose existence we assume, from the defining $`q`$-functional equation, is to insert the Ansatz (2.2) into the functional equation, introduce the scaling variable $`s=(x_cx)(1q)^\varphi `$ and expand the functional equation to leading order in $`ϵ=1q`$. This will, to lowest order in $`ϵ`$, result in a differential equation for the scaling function $`F(s)`$. Above method is also called method of dominant balance . Note first that the expansion of the generating function with $`q`$-shifted argument is given to leading order by

$$G(q^kx,q)=G^{(reg)}(x,q)+ϵ^\theta F(s)+kx_cϵ^{\theta +(1\varphi )}F^{}(s)+𝒪(ϵ^{\theta +2(1\varphi )}).$$
(3.3)
We will analyse the case of a square-root singularity of the perimeter generating function in detail. (The case of a simple pole is discussed in ). It imposes the restrictions

$$P=0,\left(\underset{k}{}_kP\right)=0,\left(\underset{k,l}{}_{k,l}P\right)0,\left(_xP\right)0$$
(3.4)
on the functional equation, evaluated at $`(x,q)=(x_c,1)`$. We introduced the abbreviations $`_k=_{y_k}`$ and $`_{k,l}=_{y_k}_{y_l}`$ for $`0k,lN`$. The assumption of a square-root singularity also implies $`\varphi =2\theta `$ for the critical exponents, as follows from the relation $`\theta +\varphi \gamma =0`$. The functional equation then has an expansion of the form

$$0=ϵ^{2\theta }\frac{1}{2}\left(\underset{k,l}{}_{k,l}P\right)F^2(s)+ϵ^{\theta +(1\varphi )}x_c\left(\underset{k}{}k_kP\right)F^{}(s)ϵ^\varphi \left(_xP\right)s+\mathrm{}$$
(3.5)
to lowest orders in $`ϵ`$. In order to obtain a non-trivial equation for the scaling functions, we demand equality of the coefficients. This results in exponents $`\theta =1/3`$ and $`\varphi =2/3`$, and we get the Riccati equation

$$F(s)^24f_1F^{}(s)f_0^2s=0,$$
(3.6)
where the coefficients $`f_0`$ and $`f_1`$ are given by

$$f_0^2=\frac{\left(_xP\right)}{\frac{1}{2}\left(_{k,l}_{k,l}P\right)},4f_1=x_c\frac{\left(_kk_kP\right)}{\frac{1}{2}\left(_{k,l}_{k,l}P\right)}.$$
(3.7)
The equation, together with the prescribed asymptotic behaviour, has the unique solution

$$F(s)=4f_1\frac{d}{ds}\mathrm{ln}\text{Ai}\left(\left(\frac{f_0}{4f_1}\right)^{2/3}s\right),$$
(3.8)
where $`\text{Ai}(x)=\frac{1}{\pi }_0^{\mathrm{}}\mathrm{cos}(t^3/3+tx)𝑑t`$ is the Airy function. The scaling function is regular at the origin, and its first singularity on the negative real axis is a simple pole, located at $`\left(\frac{f_0}{4f_1}\right)^{2/3}s_c=2.338107\mathrm{}`$ .

It is important to notice that the functional form of the result is independent of the detailed form of the functional equation, as long as the coefficients $`f_0`$ and $`f_1`$ are nonzero and finite! Thus, the scaling behaviour is determined by the type of singularity of the perimeter generating function. This remarkable kind of universality allows us to conjecture the functional form of the scaling function for self-avoiding polygons: Together with the (numerical) observation that the perimeter generating function of the model of $`\mathrm{𝑟𝑜𝑜𝑡𝑒𝑑}`$ SAPs $`G^{(r)}(x,q)=x\frac{d}{dx}G(x,q)`$ also has a square-root singularity, one might ask if it has the scaling function (3.8).

## 4 Bar-graph polygons

The model of bar-graph polygons has been defined and solved exactly in . We review the derivation and extract the scaling behaviour as outlined above. Let $`G(x,y,q)`$ denote the anisotropic perimeter and area generating function for bar-graph polygons. The variable $`q`$ is conjugate to the area, while the variables $`x`$ and $`y`$ are conjugate to the horizontal and vertical perimeters respectively. By partitioning the set of bar-graph polygons into subsets of inflated and concatenated ones, it is straightforward to show that $`G(x,y,q)`$ satisfies a $`q`$-quadratic functional equation in the horizontal perimeter variable $`x`$ and the area variable $`q`$

$$G(x,y,q)=G(qx,y,q)qxG(x,y,q)+yG(qx,y,q)qx+yG(qx,y,q)+qxG(x,y,q)+yqx.$$
(4.1)
This is depicted in Figure 2.

The $`q`$-quadratic functional equation can – similarly to the treatment of a Riccati differential equation – be linearised by means of the transformation

$$G(x,y,q)=\frac{y}{qx}\left(\frac{H(qx,y,q)}{H(x,y,q)}(1+qx)\right),$$
(4.2)
and the resulting $`q`$-linear functional equation of order two for $`H(x,y,q)`$ can be solved by iteration. This leads to

$$H(x,y,q)=\underset{n=0}{\overset{\mathrm{}}{}}\frac{(qx(1y))^nq^{\left(\genfrac{}{}{0pt}{}{n}{2}\right)}}{(q;q)_n(y;q)_n},$$
(4.3)
where $`(t;q)_n=_{k=0}^{n1}(1tq^k)`$ denotes the $`q`$-product. The appearance of a $`q`$-series is a generic feature of solutions of $`q`$-algebraic functional equations, making it difficult to extract the asymptotic behaviour for $`q1`$ directly from an exact solution. For staircase polygons, the first exactly solved model with a $`q`$-quadratic functional equation , this has been done by use of saddle point techniques , and this method can also be applied to the above solution. A more direct approach consists in deriving the (anisotropic) scaling function directly from the defining functional equation by use of the above methods. To this end, note that the defining polynomial is of the form $`P(z_0,z_1,x,q)=qxz_1z_0+(1+qx)yz_1+(qx1)z_0+qxy`$. The perimeter generating function may be found by setting $`q=1`$ and solving the functional equation for $`G(x,1)`$. It has a square-root singularity at $`x_c(y)=\frac{1+y2\sqrt{y}}{1y}`$. An analysis along the above lines yields

$$f_0^2=\frac{(1y)^2(1x_c(y)^2)}{4x_c(y)^3},4f_1=\frac{1}{2}\left(1+y(1y)x_c(y)\right),$$
(4.4)
and the scaling function is the logarithmic derivative of an Airy function, given by (3.8). The critical exponents are $`\theta =1/3`$ and $`\varphi =2/3`$.

## 5 Self-avoiding polygons

The model of rooted SAPs, $`G^{(r)}(x,q)=x\frac{d}{dx}G(x,q)`$, has been analysed numerically some time ago, where it was found to exhibit the same exponents $`\theta =1/3`$ and $`\varphi =2/3`$ as bar-graph (staircase) polygons which, in particular, implies a square-root singularity of the perimeter generating function (see also ). With the improved series data now at hand and the refined techniques of analysis, we were able to confirm our conjecture about the scaling function to high precision using data obtained from exact enumeration for small values of perimeter, on the square lattice and on the triangular lattice . In addition, it allowed us to analyse the first two corrections to scaling . Here, we present results obtained from an analysis of extended enumeration data for square, hexagonal and triangular lattices and in addition we present data for the square lattice obtained from Monte-Carlo simulations. The underlying assumption is that the scaling behaviour of rooted SAPs may be arbitrarily well approximated by the scaling behaviour of solutions to a $`q`$-algebraic functional equation with a square-root singularity. The scaling function (3.8) implies certain relations between the amplitudes $`f_k`$ of the leading singularity (2.5) of the area moment functions $`g_k(x)`$. Using the Riccati equation (3.6) for the scaling function, it can be shown that $`f_n=c_nf_1^nf_0^{1n}`$, where the numbers $`c_n`$ are given by the quadratic recursion

$$c_n+(3n4)c_{n1}+\frac{1}{2}\underset{r=1}{\overset{n1}{}}c_{nr}c_r=0,c_0=1.$$
(5.1)
The first few values are $`c_1=1`$, $`c_2=5/2`$, $`c_3=15`$, $`c_4=1105/8`$, $`c_5=1695`$, $`c_6=414125/16`$, $`c_7=472200`$, $`c_8=1282031525/128`$, $`c_9=242183775`$, $`c_{10}=1683480621875/256`$. The coefficients $`f_k`$ may be estimated from series enumeration data: Assuming an asymptotic growth of coefficients of the area moment functions $`g_k(x)`$ of rooted SAPs of the form

$$[x^m]g_k(x)(1)^kE_kx_c^mm^{\gamma _k1}(m\mathrm{})$$
(5.2)
implies a singular behaviour of $`g_k(x)`$ of the form (2.5) with $`f_k=(1)^k\frac{E_k}{\sigma }x_c^{\gamma _k}\mathrm{\Gamma }(\gamma _k)`$ and $`\gamma _k=(3k1)/2`$. The constant $`\sigma `$ is defined such that $`p_{m,n}`$ is nonzero only if $`m`$ is divisible by $`\sigma `$. Thus $`\sigma =2`$ for the square and hexagonal lattices and $`\sigma =1`$ for the triangular lattice. Note that the amplitudes $`E_k`$, defined by (5.2), take the same values for rooted SAPs and for (ordinary) SAPs. Extrapolation techniques allow us to estimate $`x_c`$, $`\gamma _k`$ and $`E_k`$ to high precision. This route was followed in  where we used series data from exact enumeration up to perimeter 86 on the square lattice and up to perimeter 29 on the triangular lattice, where the same behaviour (5.2) is expected due to universality.

Since then the enumeration of area-moments for square lattice SAPs has been extended to perimeter 100 (110) , and series have been derived for the hexagonal lattice to perimeter 140 (156) and the triangular lattice to perimeter 58 (60) , where the numbers in parenthesis refer to slightly longer series calculated for the perimeter generating function. Details of analysis can be found in  and a brief summary will suffice here. Estimates for the critical points and exponents are obtained using the numerical technique of differential approximants . For the square and hexagonal lattices, where $`\sigma =2`$ and only coefficients with $`m`$ even are non-zero, we actually analyse the functions $`h_k(y)=_{m0,n}n^kp_{2m+j,n}y^m`$, where $`j=4`$ and 6 is the perimeter of the smallest SAP on the square and hexagonal lattices, respectively. A singularity at $`x=x_c`$ in $`g_k(x)`$ thus becomes a singularity at $`y=x_c^2`$ in $`h_k(y)`$. The generating functions for the square and triangular lattices show no convincing signs of singularities other than the one at $`x_c`$. In these cases we fit the coefficients to the assumed form

$$\underset{n}{}n^kp_{m,n}x_c^mm^{\gamma _k1}k![E_k+\underset{i0}{}a_i/m^{1+i/2}](m\mathrm{}).$$
(5.3)
In the hexagonal case $`h_k(y)`$ has an additional singularity on the negative axis at $`y=x_{}^2=0.412305(5)`$ with exponents which appear to equal the exponents at $`y=x_c^2=0.2928932\mathrm{}`$, as first noted in . Since $`x_{}>x_c`$ the singularity at $`y=x_{}^2`$ is exponentially suppressed as $`m\mathrm{}`$, however for small values of $`m`$ it still has a significant influence on the coefficients in the generating functions and we have to add an extra sequence to the fit similar to (5.3):

$$(1)^{m/2}|x_{}|^mm^{\gamma _k1}k![E_{}+\underset{i0}{}b_i/m^{1+i/2}].$$

We obtain several data sets by varying the number of terms used in the fit. Only the even coefficients are used in these fits for square and hexagonal SAPs. To obtain the final estimates we do a simple linear regression on the data for the amplitudes as a function of $`1/m`$ extrapolating to $`1/m0`$. We estimate the error in the amplitude from the spread among the different data sets. In this way, we obtain the results for the amplitude combinations listed in Table 1, which have been shown to be independent of the underlying lattice . The scaling function prediction for these numbers is

$$E_{2k}E_0^{2k1}=\frac{c_{2k}}{4\pi ^{3k}}\frac{(3k2)!}{(6k3)!},E_{2k+1}E_0^{2k}=\frac{c_{2k+1}}{(3k)!\pi ^{3k+1}2^{6k+2}}$$
(5.4)
for $`k`$, where we used the known result that $`E_1=\frac{1}{4\pi }`$ , and the numbers $`c_k`$ are defined in (5.1). It is clear that the estimates for the first 10 area weighted moments are in perfect agreement with the predicted exact values.

We also extended our previous approach by analysing SAPs up to perimeter 2048 by a Monte-Carlo simulation. An effective method of Monte-Carlo SAP generation of a given perimeter $`m`$ has been described in . Each MC step consists of an inversion or a certain reflection of a randomly chosen part of the SAP. Polygons which are no longer self-avoiding are rejected. The check for self-avoidance (by marking the corresponding lattice points) as well as the area determination (“on the fly”) can be done in time proportional to the polygon length. For a given perimeter $`m`$, we took a sample of $`10^6`$ polygons, with at least $`10\times m`$ MC update moves between consecutive measurements. This leads to an estimated statistical error of 1 part in 1000. For perimeter 2048, this took two days of CPU time on a 1.5 GHz PC. We used the random number generator ran2 described in . From the Monte-Carlo measurements of polygons of a given perimeter $`m`$, we extracted ratios $`D_k/D_1^k`$ of the mean area moment amplitudes $`D_k`$ defined by

$$a^k_m=\frac{_nn^k\stackrel{~}{p}_{m,n}}{_n\stackrel{~}{p}_{m,n}}D_kk!m^{2k\nu }(m\mathrm{}),$$
(5.5)
where $`\stackrel{~}{p}_{m,n}`$ is the number of sampled polygons of area $`n`$, and $`\nu =3/4`$ follows from (5.2). Note that by using MC sampling we cannot measure the coefficients $`E_k`$ of (5.2) directly but only the ratios $`D_k=E_k/E_0`$. We tested the accuracy of the random number generator by comparing values for the area moments obtained by simulation with their exact values, which are available up to perimeter 100 from exact enumeration. Assuming the above scaling function results, for $`k`$, in the values for the amplitude ratios

$$D_{2k}/D_1^{2k}=c_{2k}\frac{(3k2)!2^{4k2}}{(6k3)!\pi ^k},D_{2k+1}/D_1^{2k+1}=c_{2k+1}\frac{1}{(3k)!2^{2k}\pi ^k},$$
(5.6)
where the numbers $`c_k`$ are defined in (5.1). We computed the values $`a^k_m/(k!a_m^k)`$ for $`m=64,96,128,192,256,512,1024,2048`$, and a typical data plot is shown in Figure 3.

We then extrapolated the numbers $`D_k/D_1^k`$ by a least squares fit to $`a^k_m/(k!a_m^k)D_k/D_1^k+c_1m^1+c_2m^{3/2}`$ as $`m\mathrm{}`$, in analogy with the series extrapolation for exact enumeration data. The corresponding results for the first ten amplitude combinations are given in Table 2, together with their theoretical values. The relative error is less than 1 part in 1000.

The value of $`D_1`$ is estimated to be $`D_10.141776`$. We can compare this to our previous analysis by noting that $`D_1=E_1/E_00.14152105(1)`$, where $`E_1=\frac{1}{4\pi }`$ has been derived by conformal field theory arguments , and $`E_0=0.56230130(2)`$ together with $`x_c=0.379052277757(5)`$ has been determined in . Noting that $`f_0=2\frac{E_0}{\sigma }\sqrt{\frac{\pi }{x_c}}`$ and $`f_1=x_c\frac{E_1}{\sigma }=\frac{x_c}{4\pi \sigma }`$ we arrive at the conjectured form of the scaling function for rooted SAPs

$$F^{(r)}(s)=\frac{x_c}{\pi \sigma }\frac{d}{ds}\mathrm{log}\text{Ai}\left(\frac{\pi }{x_c}\left(2E_0\right)^{\frac{2}{3}}s\right)$$
(5.7)
with exponents $`\theta =1/3`$ and $`\varphi =2/3`$. (Formula (22) in  is correct up to a minus sign.) The conjectured form of the scaling function is then obtained by integration and is

$$F(s)=\frac{1}{\pi \sigma }\mathrm{log}\text{Ai}\left(\frac{\pi }{x_c}\left(2E_0\right)^{\frac{2}{3}}s\right)$$
(5.8)
with exponents $`\theta =1`$ and $`\varphi =2/3`$. The parameters for the hexagonal lattice are $`\sigma =2`$ and $`x_c=1/\sqrt{(2+\sqrt{2})}`$ (known exactly from the work of Nienhuis ) and for the triangular lattice $`\sigma =1`$ and $`x_c=0.2409175745(3)`$.

## 6 Conclusion

We discussed the scaling behaviour of $`q`$-algebraic functional equations which underlie the critical behaviour of exactly solvable planar polygon models, counted by perimeter and area. This led to a prediction of the scaling function of the unsolved model of self-avoiding polygons on the square lattice, which we verified to numerical precision. The prediction also implies certain amplitude combinations for all area moments. It was previously argued  that these combinations should be universal, i.e., independent of the underlying lattice. Our investigations on the triangular and on the hexagonal lattices support the universality hypothesis, see also . It is possible to extend the above analysis to include the first few corrections to scaling .

The question arises whether the SAP area statistics can be found in other models as well. One candidate is the hull of planar Brownian motion, which was observed in 1984 to have the same fractal dimension as SAPs . Interestingly, this observation has been proved recently using methods of stochastic processes . It might thus be possible to derive the area distribution rigorously for this model, as well as a corresponding prediction for the SAP area distribution.

Since $`q`$-algebraic functional equations are the underlying mathematical structure of (exactly solvable) planar polygon models counted by perimeter and area, they may serve to classify possible scaling behaviour of these polygon models. $`q`$-algebraic functional equations exhibit various types of scaling behaviour, depending on the specific type of singularity of the perimeter and area generating function . Since the techniques applied so far only make use of formal power series expansions, one might ask for a proof of existence of a uniform asymptotic expansion. Details of a proof may rely on techniques used in the related problem of the behaviour of differential equations containing a parameter  about singular points. Recently, the scaling function prediction has been rederived using field-theoretic methods and generalised to higher order critical points . It would be interesting to see whether the proposed scaling functions of  arise in this framework as well. It may be possible that $`q`$-algebraic functional equations also provide insight into models of polygons with interaction, $`q`$ then being the activity of interaction. There is at least one such exactly solvable model: self-interacting partially directed walks .

Another possible application might be to models of cluster hulls, which appear in percolation or in spin models as boundaries of spin clusters in the Ising model or in the Potts model, as described in .

## Acknowledgements

CR would like to acknowledge financial support by the German Research Council (DFG). IJ and AJG would like to acknowledge the Australian Research Council (ARC) and IJ would also like to thank the Australian Partnership for Advanced Computing (APAC) and the Victorian Partnership for Advanced Computing (VPAC) for generous allocations of computational resources.


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# Exceptionally Slow Rise in Differential Reflectivity Spectra of Excitons in GaN: Effect of Excitation-induced Dephasing

## I Introduction

Group III nitride semiconductors such as GaN and InGaN have become important materials owing to their optoelectronic device applications in the blue and ultraviolet spectral range and their use in high temperature electronic devices. The demonstration of InGaN multiple quantum well laser diodesNakamura  has also inspired tremendous research interest in the nitride-based materials. Transient four-wave mixing (FWM) studies on GaN were performed to investigate the intrinsic excitonic propertiesFischer ; Pau  and the influence of electron spins on exciton-exciton interactionGonokami . Femtosecond pump-probe (P-P) measurements were done by C.-K. Sun et al. on InGaNSun1  and n-doped GaNSun2  to investigate the fast carrier cooling. Time-resolved studies of coherent acoustic phonons in GaN and GaN/InGaN systems Sun99 ; Sun2000 ; Yahng1 ; Stanton2002 , as well as coherent optical phononsYee2002  were performed. Recently, field dependent carrier decay dynamics were done by Jho et al.Jho2001 ; Jho2002

In the FWM experiments on GaN, quantum beats of excitons and their phase changes via polarization configurations have been studied and exciton-phonon interaction rates were deduced. Nevertheless, there are still not a lot of time-domain studies regarding the coherent response of excitons in GaN including many body effects.

The FWM line shapes not only discriminate between homogeneous broadened and inhomogeneous broadened systemsFischer  but also provide information on the carrier-carrier interactionShah . For instance, time-integrated (TI) FWM signals at negative time delays have been observed in GaAs quantum wellsWegener ; Leo  and understood by local-field effectsWegener ; Leo  or excitation-induced depasing (EID)Wang  which are incorporated into the semiconductor Bloch equations. In addition, it was argued that EID dominates at a moderately low exciton density ($`<`$ $`10^{16}cm^3`$) and gives a strong contribution to TI-FWM in the co-linearly polarized geometry.Wang

In this work we report the comparative studies of femtosecond degenerate pump-probe (PP) differential reflectivity spectroscopy (DRS) measurements and time-integrated (TI)-FWM experiments on GaN epilayers as a function of excitation energy at low carrier excitation density. In addition, we have also performed PP differential transmission spectroscopy on a thin GaN sample, though not simultaneously with FWM. Our results show that the quantum beats as revealed in previous studiesFischer ; Pau ; Gonokami  are the same both in PP and FWM and exist only for positive time delay. Results further show that the DRS and FWM differ at negative time delays, with the DRS signal persisting longer at the negative delays in spite of inhomogenous broadening. Calculations based on a six-band semiconductor Bloch equation model solved in the Hartree-Fock level show that this difference arises from EID, that is, the dephasing time depends on the carrier density excited by the laser pulse.

## II Experimental scheme

The GaN samples used in this work were a 7.2 $`\mu `$m-thick and a 2 $`\mu `$m-thick epilayer grown with the wurtzite structure on a (0001) sapphire substrates by metalorganic chemical vapor deposition. The second harmonic of a femtosecond Ti-sapphire laser in the high-energy region of the tuning (705 nm - 710 nm) was used, with 150-fs pulse-width. As shown in the Fig. 1(a), we have performed both FWM and differential reflectivity spectroscopy (DRS) simultaneously in the reflection geometry on 7.2 $`\mu `$m-thick sample. To compare the differential reflection spectra with the differential transmission spectra (DTS), a 2 $`\mu `$m-thick sample was also used. The pump and probe pulses were at the same wavelengths and collinear polarization. All measurements were performed at 11 K unless otherwise noted (c.f. Fig. 7). To reduce the effect of the laser noise, we used a differential amplification scheme after dividing the probe beam ($`𝐤_\mathrm{𝟏}`$) into two. With this scheme, the DRS signal can be as small as $`10^4`$.

In Fig.1(b), the spectrally resolved (SR) FWM data (solid line) at 11 K is shown together with the spectrum of laser for detunings of 0 meV (dashed) and 20 meV (dotted) from the center of the exciton peaks. There is no time delay between pump and probe. The two peaks of Fig. 1 (b) correspond to the $`\mathrm{\Gamma }_9^V\mathrm{\Gamma }_7^C`$ exciton (A exciton transition) and the $`\mathrm{\Gamma }_7^V\mathrm{\Gamma }_7^C`$ exciton (B exciton transition), which are caused by crystal field and spin-orbit coupling. The dashed and dotted lines are the spectrum of laser at the center of the exciton resonances and at 20 meV above the resonance. The linewidth of peaks are measured to be 2.1 meV for the A exciton, and 2.5 meV for the B exciton. The energy difference of the two excitons is about 8 meV.

The power of the pump (probe) pulse which is in the reflection direction of $`𝐤_\mathrm{𝟏}`$ ($`𝐤_\mathrm{𝟐}`$) was 0.5 mW (0.1 mW). The two beams are focused onto a 100 $`\mu `$m spot with the external-crossing angle of $`6^o`$. From the measured absorption coefficient, we estimate the initial carrier density to be $`5\times 10^{15}cm^3`$ at the center of the exciton resonances (3.497 eV)Fischer2 . There was no detectable change of decay time in the FWM for carrier densities ranging from $`10^{15}cm^3`$ to $`5\times 10^{16}cm^3`$.

## III Results and discussion

Fig. 2 shows the simultaneous measurements of the DRS and FWM at the excitation energy of (a) 3.497 eV, (b) 3.507 eV, and (c) 3.517 eV. The FWM data were scaled with the DRS data for comparison. In both the PP and FWM data, the strongest signal was observed at the exciton resonance, 3.497 eV. This is in the middle of the A and B excitons. Here $`\mathrm{\Delta }`$, the detuning is chosen to be the energy above 3.497 eV and hence the figures correspond to detunings of $`\mathrm{\Delta }=0,10`$ and $`20`$ meV respectively. The PP data and the FWM, in positive time delay, show similar features, namely that of beating between the A and B excitons. This beating is strongest for $`\mathrm{\Delta }=0`$, i.e. at the resonance and has a period of about 500 fs. This period is consistent with the SR-FWM that showed the energy difference of 8 meV between A and B excitons (c.f. Fig. 1).

One puzzling difference between the PP DRS and FWM signals is the behavior at negative time delay. The PP signals in negative time delay persist much longer than the FWM and do not show the A-B exciton beatings. The DRS behavior is strongest at the exciton resonance ($`\mathrm{\Delta }=0`$), but becomes less pronounced as one increases the detuning ($`\mathrm{\Delta }=`$ 20 meV) and excites further into the band. The values of the DRS rise times obtained from first order exponential fits were 445 fs ($`\mathrm{\Delta }=0`$), 381 fs ($`\mathrm{\Delta }`$= 10 meV), and 183 fs ($`\mathrm{\Delta }`$=20 meV). The error in determining the rise time is less than 20 fs for all measurements. The rise times of FWM were less than 200 fs for all excitation energies and comparable to the pump laser duration.

The fact that there is a fast rise time in negative delay in the FWM is not surprising. To see a slow rise in the FWM signal in the negative time delay requires that the sample be very clean and that inhomogeneous broadening is weak.Wegener ; Leo  Inhomogeneous broadening will wash out any negative time signal in the FWM.

In Fig. 3 we compare the rise times of the DRS versus the FWM signal. Since the values of FWM decay time ($`\tau _{FWM}`$) for positive delay and zero detuning ($`\mathrm{\Delta }=0`$) in Fig. 3 are at least three times larger than the FWM rise times, this indicates that the spectra are inhomogeneously broadened in these samples.Fischer ; Wegener  In fact, the rise time of the FWM signal appears to be limited by the pulse duration, again consistent with strong inhomogeneous broadening. As a result, one would not expect to see a FWM signal in the negative time delay since it has been shown that this would occur only in a homogeneously broadened system.Wegener ; Leo

In contrast, the differential pump-probe reflectivity spectra can have a signal at negative delay, even with inhomogeneous broadening. This is related to the free polarization decay (FPD) of the probe pulse which plays a role in the DRS signal at negative time delays. Note however, that the FPD of the probe pulse does not effect the FWM. This is because while the FPD of the probe pulse will produce a signal in the probe direction ($`𝐤_\mathrm{𝟐}`$), it does not produce a signal in the FWM direction $`\mathrm{𝟐}𝐤_\mathrm{𝟐}𝐤_\mathrm{𝟏}`$.Leo

The FPD persists when the probe precedes the pump even in an inhomogeneously broadened system. This leads to a rise time with an effective time constant $`T_2^{}`$. $`T_2^{}`$ is given approximately by the inverse of frequency spread due to inhomogeneous broadening $`1/\mathrm{\Delta }\omega `$ and is shorter than $`T_2`$, the homogeneous dephasing time.Brito  If the pump pulse (which is now after the probe pulse for negative time delay) overlaps with the tail of the FPD of the probe pulse, then it may be possible to produce a signal in the probe pulse.

It has been shown in DTS, that the overlap of the pump with the tail of the probe polarization generates a transient diffraction grating with wavevector $`𝐤_\mathrm{𝟐}𝐤_\mathrm{𝟏}`$. This transient grating can lead to a diffraction of part of the pump pulse with wave vector $`𝐤_\mathrm{𝟏}`$ into the probe direction $`𝐤_\mathrm{𝟏}+(𝐤_\mathrm{𝟐}𝐤_\mathrm{𝟏})`$. This is the qualitative origin of the well-known coherent oscillations in semiconductorsKoch  or the perturbed free polarization decay termBrito . The spectral oscillations induced from the transient grating have no correlation with the exciton oscillations seen in Fig. 2(a) at positive time delay. These coherent oscillations are readily observed in our sample, and are shown in Fig. 4 for the spectrally resolved DRS signal. The spectral oscillations, depend on the time delay as well as the detuning from the exciton resonance.

However, a solution of the density matrix equationBrito  without incorporating the exciton-exciton interaction or EID, shows that, when integrated over frequency, the different spectral oscillatory signals cancel out and the net result is that DTS spectra at each negative time delay is integrated out to be zero. This result should also hold for the DRS spectrum when the excitation is deep within the band continuum. In fact, Fig. 2(c) precisely shows this effect. (In addition, for large detuning and excitation within the band, the dephasing time $`T_2`$ should be much shorter than for excitations between the A and B excitons).

Below the continuum band edge, the situation is more complex. To study this effect more thoroughly, calculations were performed based on the Semiconductor Bloch Equations.

## IV Calculations

To better understand the origin of the slow rise-time of the DRS signal in Fig. 2, we have calculated both the differential reflection (DRS) and differential transmission spectra (DTS) by solving a coupled six-band semiconductor Bloch equation modelKenrow ; Hu  including all Hartree-Fock nonlinearities. From the semiconductor Bloch equations, the dielectric response is calculated. Typically, the reflection is much more sensitive to the real part of the dielectric response while the transmission is more sensitive to the imaginary part of the dielectric response. In our calculations, we have included carrier scattering on a phenomenological level to allow for the relaxation of the photo-excited carriers back to equilibrium. In addition, we have included excitation induced dephasing (EID)Sayed ; Wang  to allow for the change in the carrier dephasing time as the density of excited carriers changes with the pump laser pulse.

In the framework of EID, the inverse polarization decay time is given by

$$1/T_2=\mathrm{\hspace{0.17em}1}/T_{2,0}+n/T_{2,1},$$
(1)
and is a linear function of the induced carrier density, $`n`$. $`T_{2,1}`$ corresponds to the carrier-carrier scattering time as the carriers are photoexcited in a nonthermalized distribution. At low carrier densities, scattering such as electron-electron is a linear function of the density. At higher densities, screening effects can become important and change the density dependence. Note that the polarization decay time has the important property that it is long when the probe proceeds the pump since no carriers have been created yet and the decay time becomes shorter when the probe comes after the pump pulse which creates photoexcited carriers.

We chose the low density dephasing time, $`T_{2,0}`$ to be 1 ps. By numerically integrating the semiconductor Bloch equations, we computed the induced polarization with and without the pump pulse present. The corresponding dielectric response, which determines the reflection and transmission spectra, is obtained from the Fourier transform of the probe polarization.

In calculating the dielectric response, we do not allow for intraband changes to the dielectric function. This should be less important when one excites below the band edge since there are no free carriers available to screen out the laser pulse and give a Drude-like contribution to the dielectric function, which can be important in the reflectivity. However, this becomes more important when a large number of free carriers are excited above the band gap and for strong excitation above the gap, may even dominate the signal.Zollner1 ; Zollner2  In addition, we do not include diffusion of carriers away from the surfaceZollner1 ; Zollner2 ; Bailey  of the sample in our calculations. The intent of the calculations is to understand the initial behavior of the PP DRS and DTS spectra. Diffusion effects become important on a time scale longer than 1 ps and should be included along with more accurate scattering models in more detailed studies for longer times.

Results of the numerical solution to the model are shown in figure 5. Figure 5 shows the computed DTS and DRS signals as a function of delay between the pump and probe pulses. Fig. 5 (a) gives the result when the pump and probe are both at resonance with the excitons (excitation between the A and B excitons) and EID as well as carrier scattering are included (i.e. both terms in eq. 1). The corresponding results when EID was excluded (i.e., only the first term on the left hand side of eq. 1 is included) are shown in Fig. 5(b). Note that both figures show the oscillations resulting from A and B exciton beating in both the DRS and DTS signals at postive time delay.

Our simulation also reproduces the slow rise-time of the DRS signal in Fig. 2(a) only if EID is included (cf. Fig. 5(a)). However, if EID is excluded, the effect vanishes and the signal strength is diminished by 60 % (cf. Fig. 5(b).) In this case, oscillations occur at negative time in the in the DRS. It is important to note that this behavior is not seen for the corresponding DTS signal where the rise times are unaffected by EID. However, a comparison of the two DTS signal strengths shows that the inclusion of the EID enhances the signal strength by 40%. When probing the samples at laser energies deep into the band, (Fig. 5(c)) we find that the rise time of the DRS signal is now faster in agreement with experiment (cf. Fig. 2, 3), and shows little difference with the DTS signal. Of course, deep within the band, one must take into account the other effects previously mentioned.

In addition to calculating the PP DRS and DTS signals, we have also calculated the FWM signal. The calculations agree with the experimental results of Fig. 2 showing: (i) the decay of the FWM signal as one increases the detuning, $`\mathrm{\Delta }`$ and excites further into the band, (ii) that that the EID does not change the rise-times of the FWM at the exciton energy or in the band, and (iii) that the oscillations in the FWM for positive time delay are out of phase with the oscillations in the DRS. Similar results were also seen in calculations of the FWM in high-quality GaAs quantum wells.Sayed

To investigate futher our theoretical prediction that the DRS signal shows a slow rise time while the DTS signal shows a fast rise time, further experimental pump-probe measurements were performed in both the reflection and transmission geometry on bulk GaN. To be able to perform transmission measurements, the 2 $`\mu `$m thick samples were used. The results are shown in Fig. 6. The excitation spectrum was chosen to excite both the A and B exciton simultaneously. The temporal traces of the DRS and DTS show the qualitative behavior similar to our theoretical calculations including EID; a much slower rise time in the DRS as opposed to the more rapid, pulse-form limited rise of the DTS. Note that there is a negative dip in DTS near zero delay. This can possibly be caused by distortion of the pulse.Kim  We note that the thickness of 2 $`\mu `$m is much larger than the penetration depth of GaN, hence, any excitonic signals must have been absorbed and the DTS signal is an order of magnitude larger than DRS signal due to relatively small transmission compared to the pump induced transmission change.

One possible reason for the differences in the early time behavior of the DTS versus the DRS signals is that they measure different quantities. The DTS signal is related to the imaginary part of the dielectric function which is a local function of frequency depending on the central frequency of the probe pulse. The DRS depends more strongly on the real part of the dielectric function. Hence, through the Kramers-Kronig transformation, the DRS is sensitive to spectral regions above and below the central probe frequency.

In Fig. 7 we investigate the temperature dependence of the DRS and FWM for $`\mathrm{\Delta }=0`$. The polarization decay time is given by the eq. 1. The first term on the right represents decay due to scattering with impurities or phonons which is not strongly density dependent and the second term represents the density dependent scattering mechanisms such as carrier-carrier (electron-electron, electron-hole etc). We expect the first term to be much more temperature dependent since, for example, electron- phonon scattering depends on the phonon occupation number which depends strongly on temperature. Carrier-carrier scattering is only weakly temperature dependent. Fig. 7 shows the data of the DRS (solid lines) and TI-FWM (dotted lines) measured at four different temperatures (T=11, 70, 110, and 150 K). The laser was tuned to excite both the A exciton and B exciton. We note that as the temperature is increased, the rise time at negative delay of the DRS becomes more rapid and approaches that of the FWM. We see that near 150K , both the DRS and FWM have nearly the same rise time. In addition, the DRS rise time and FWM decay time (for positive delay) show a similar tendency to decrease with increasing temperature. The rapid decrease of FWM decay time starting from around 150 K is due to the dominance of optical phonons as a scattering mechanism for dephasing of excitons.Fischer  Note that the rapid phonon scattering time above 150 K also has the effect of rapidly damping out the FPD and hence the DRS signal now has a fast rise time.

Our theoretical results based on EID are suitable only for the low density regime where the nonlinear response near the band edge is dominated by excitonic screening of the carrier-carrier Coulomb potential.Wang  As we increase the carrier density ten-fold as shown in Fig. 8, EID is not dominant any more and the slow rise signal which was observed in Fig. 2 is superimposed by a faster rise with opposite sign. The sign change in Fig. 8 could possibly be associated with the band-gap renormalization and reduction of the Coulomb enhancement factor which occurs for high density photoexcitation.Sun1 ; Langot

## V Conclusion

In this work, we have studied the initial temporal dynamics in GaN epilayers through the simultaneous measurement of PP DRS and FWM. For resonant excitation of the A and B excitons, we have observed an unusually slow rise time in negative time delay only in the PP DRS in contrast to the FWM and DTS signals which show a more rapid rise time. These differences can be explained by excitation induced dephasing and the fact that the FPD of the probe pulse can contribute to the PP signal, but not the FWM. We have shown from simulations of the Semiconductor Bloch Equations, that EID strongly alters the line-shape for the DRS signal. With no scattering or excitation induced dephasing, the negative time delay in the DRS shows oscillations. With scattering and EID, we obtain a slow rise time at the exciton resonance for the DRS but not for the FWM or DTS signal. For energies above the band edge or at higher temperature where scattering is much stronger, the DRS signal has a short rise time and the FWM signal decays rapidly even at positive delay times.

###### Acknowledgements.

This work was supported by MOST (the National Research Laboratory Program) and KOSEF (the Center for Strongly Correlated Materials Research, and Grant No. 97-0702-03-01-3). The work at U. of Florida was supported in part through Department of Energy through grant DE-FG05-91-ER45462 and the National Science Foundation through grant DMR-9817828.