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# Hexagonal microlasers based on organic dyes in nanoporous crystals

## 1 Introduction

In recent years dye laser emission from from crystalline materials attracted considerable interest RIF95 ; KAH96 . At the same time in solid state dye lasers based on polymer matrices single mode operation at high peak powers was demonstrated DUA95 , and photodegradation processes were identified POP99 . Recently, we reported on microscopic dye lasers, in which the active molecules were embedded in crystallographically defined nanometer size pores of molecular sieves VIE98 . In the past, such nanoporous materials, e.g. zeolites, proved to be pertinent especially to the catalysis in oil refining and petrochemistry, where they are used in huge amounts. It is only recently that applications of this class of porous crystalline material are discussed in an optical context. In fact, molecular sieves can be used to host a wide variety of optically relevant guests, such as atoms, ions, or molecules STU90 . Sieves with tubular or channel pores, in particular, can act as an ordering framework for guest molecules SUL94 . For optical applications it is possible to exploit thus distinct spatial symmetries in the arrangement of organic molecules, enhancing so, for example, the second order nonlinear susceptibility of the compound COX88 , or admitting anisotropic Förster energy migration GFE98 . Nanoporous crystals were also studied as hosts for luminophores BRE91 , pigments BRA97 , optical switches HOF97  or dye lasers VIE98 . In the following we report about the novel emission properties of hexagonal monolithic microresonators realized with dyes intercalated in molecular sieve microcrystals, and the photostability of these systems.

## 2 Material

### 2.1 Host crystal

Molecular sieve materials are characterized by a crystallographically defined framework of regularly arranged pores. In table 1 we list some sieves, which, owing to their large diameters of channel pores, are suitable for hosting optically effectual organic molecules. Among the listed materials especially the aluminophosphate AlPO4-5 (molecular mass 1463.4 g/mol) can be synthesized with good optical transparency and low internal scattering losses. Its channel pores exhibit a diameter of 0.73 nm, which is large enough to accomodate suitable organic dye molecules.

AlPO4-5–crystals are crystallized from aqueous or alcoholic solutions under hydrothermal conditions, with the addition of an organic structurizing agent, called template. The template, tri-n-propylamine in our case, is necessary to direct the synthesis towards the desired structure. The preferred pH range for the synthesis is mildly acidic to mildly basic. The most utilized source of phosphore is orthophosphoric acid, and the most studied sources of aluminum are pseudoboehmite and alkoxides WIL91 . Single crystals with nearly perfect morphology were grown using hydrofluoric acid GIR95 . With a specially prepared and aged aluminum hydroxide gel crystal sizes around 1 mm in $`c`$-axis direction were obtained SUN96 , whereas microwave heating proved to increase the crystallization rates by more than one order of magnitude GIR95 ; DU97 .

Pure AlPO4-5 crystals are optically transparent from below 400 nm to above 800 nm ($`n_{500\mathrm{nm}}=1.466`$), and after removing the template (usually by heating/calcinating) they exhibit practically no birefringent properties. X-ray patterns revealed systematic absences which are consistent with space group $`\mathrm{P}\frac{6}{\mathrm{m}}\mathrm{cc}`$ as well as P6cc, whereby, however, the latter implies a polar nature of AlPO4-5 single crystals: In fact, the 4 in the formula is the result of the strict alternation of Al and P in the tetrahedral nodes of the framework, which prevents the corner-sharing oxygen tetrahedra to occur with odd numbers, and which leads to an alternating stacking of Al and P in the direction of the channels ($`c`$-axis). This is assumed to cause the crystallographic polar nature BEN83  of the framework MAR94 . The macroscopic polar nature of AlPO4-5 single crystals has been proven recently in scanning pyroelectric microscopy investigations KLA99 . There it was also observed that AlPO4-5 crystals are usually twinned. The murky stripes inside the pyridine 2-loaded crystals shown in Fig. 1 and their slightly bowed side faces could well be a result of this kind of twinning. It is not clear, however, to what extent such twinning should affect the optical properties relevant for the effects discussed here.

### 2.2 AlPO4-5/pyridine 2 compound

The compounds were synthesized following a procedure in which the dye 1-ethyl-4-(4-(p-dimethylaminophenyl)-1,3-butadienyl)-pyridinium perchlorate (cf. Fig. 2) (pyridine 2 BRA94 ) is added to the template or to the aluminum hydroxide suspension HOP93 ; DEM95 ; IHL98 . After 1 h of hydrothermal synthesis dark red crystals with a length of up to 100 $`\mu `$m were obtained. The crystals were refluxed in ethanol for 4 h whithout any detectable extraction of dye. The slim, linear dye molecules fit snugly into the 0.73 nm wide channel pores of the nanoporous AlPO4-5 host, resulting so in an ordered compound material, in which the dye molecules are all aligned along the crystal $`c`$-axis. As a consequence the compound exhibits strong dichroism, and the emitted fluorescence light is polarized parallel to the $`c`$-axis. This is documented in Fig. 1. It is also observed that with the inclusion of pyridine 2 the entire compound acquired pyroelectric properties and an optical second order susceptibility VIE98 .

Depending on the dye content different morphologies of crystals are observed. Regular hexagonal crystals with a rodlike form, as e.g. the ones shown in Fig. 1, were obtained when the dye content was low, around 0.1 wt% or 260 molecules per unit cell. At higher concentrations the dye accumulated in the middle of the crystal, and the morphology was severely disturbed. At dye content $``$ 0.2 wt% crystals with a caracteristic fascicular shape resulted; cf. Fig 3. Given the small size of the crystals we had to determine the dye content by chemically dissolving them. With this method, however, it was not possible to accurately determine the spatial distribution of the dye. We therefore evaluated the content qualitatively by comparing the depth of the color. It was only with these fascicled pyridine 2-loaded crystals that we observed laser emission. Apparently the low concentration of dye in the undisturbed rod-shaped crystals did not spoil the growth but on the one hand was not sufficient to provide the necessary optical gain for compensating all losses.

### 2.3 AlPO4-5/rhodamine BE50 compound

The synthesis gel was prepared according to recipes BEN83 ; WIL82  modified for the purpose of crystallization inclusion of dyes WOH92 . To a suspension of 61.6 mmol $`\mathrm{Al}_2\mathrm{O}_3`$ (8.44 g; Pural SB, Condea Chemie) as aluminum source and 75 g deionized water, 61.6 mmol $`\mathrm{P}_2\mathrm{O}_5`$ (14.20 g phosphoric acid; 85 wt%, p.a. Merck) in 11.3 g deionized water was added under mechanical stirring. After 5 min a uniform gel formed and then 92.4 mmol tripropylamine (13.25 g $`\mathrm{Prop}_3\mathrm{N}`$, Merck) was added slowly. Subsequently, the appropriate amount (0.1–10 mmol) of the dye powder was mixed with the gel. The new derivative rhodamine BE50 (ethanaminium, $`N`$-\[6-(diethylamino)-9-\[2-($`N,N`$-dimethyl-3-amino-1-propoxycarbonyl)phenyl\]-3H-xanthen-3-ylidene\]-$`N`$-ethyl-chloride; cf. Fig. 4) was synthesized by esterification of rhodamine B (Rh B) with 3-dimethylamino-1-propanol BOC98 . It was shown that the concentration of rhodamine BE50 (Rh BE50) achievable by crystallization inclusion in AlPO4-5 exceeds the possible Rh B concentration by a factor of 3–4. This was attributed to the different molecule structures, i.e., to the zwitterionic nature of Rh B on one hand, and to the additional positive charge of a protonated aliphatic amino group of Rh BE50 on the other hand BOC98 . The latter molecules with the localized positive charge are more compatible with the AlPO4-5 framework than the delocalized charge of Rh B. As a consequence we observe that at the same dye concentration Rh BE50 inclusion leads to a better crystal morphology than Rh B inclusion BRA99 . The synthesis of the Rh BE50/AlPO4-5 crystals was performed by microwave heating BRA98 , which has proven to be superior in respect to avoiding damage of sensitive dyes like coumarines BRA97  as well as in reducing the time of synthesis BOC98 .

Unlike the pyridine 2 molecules, which with a diameter of 0.6 nm fit into the 0.73 nm wide pores of the AlPO4-5 host, the Rh BE50 molecules with dimension of 0.91 $`\times `$ 1.36 nm2 must be accomodated in defect sites (mesopores) of the host crystal. Remarkably, up to concentrations of 1 molecule per 75 unit cells this remains without any visible negative consequences for the crystal morphology, as is documented in Fig. 5.

In Fig. 1 the dichroic properties of the compound are illustrated. In comparison with the pyridine-2/AlPO4-5 compound, the dichroism of the Rh BE50 compound is reduced and the fluorescence emission is partially polarized. Thus it is inferred that the anisotropy of the host structure does not fully carry through the mesopores, and thus the guest molecules are only weakly aligned.

## 3 Microresonator structure

As is visible in Fig. 1 – and as the polarization of the emitted fluorescence of the compounds indicates – the absorption, as well as the emission dipole moment of the included dyes are oriented preferentially along the crystal $`c`$-axis (Complete orientation in the pyridine 2/AlPO4-5 compound). As dipole emission along the dipole-axis is not possible, the emission parallel to a plane perpendicular to the prevailing dipole orientation (i.e. the hexagonal axis) is enhanced. Here a bundle of emission directions meets the condition for total internal reflection (TIR) at the hexagonal side faces inside the crystal. In a whispering-gallery-mode-like way the corresponding emission can circulate sufficiently often to accumulate the gain required to overcome the lasing threshold; cf. Fig. 6 in which this intuitive model is illustrated for a particular ray bundle of high symmetry. However, with resonator sizes in the order of a few wavelengths, as discussed here, the ray picture does not represent the field modes even in a qualitatively correct way. E.g. the ray picture insinuates a mode concentration in the center of the faces and field-free corners. However, this is not consistent with the experimental evidence, which clearly shows that the emission occurs at the corners; cf. Fig. 13. In fact, for dielectric resonator structures a few wavelengths large with TIR field confinement a wave model has to be worked out.

### 3.1 Ray picture

The main feature that distinguishes the hexagonal resonator from other common whispering-gallery type cavities such as microdroplets mekis95  or semiconductor disk lasers nature ; gmachl , is that the latter do not exhibit sharp corners and flat sides. Portions of the boundary in convex resonators can act as focussing or defocussing elements, but the straight sides of a hexagon are neither one nor the other. The hexagon in fact constitutes a self-assembled realization of a pseudointegrable resonator richensberry : For a polygon with precisely $`120^{}`$ angles between adjacent sides, any ray lauched at some angle to the surface will go through only a finite number of different orientations hobson , just as in the more familiar rectangular resonator where there are at most two non-parallel orientations for any ray path. In the hexagon, a ray encounters the interface with at most three different angles of incidence. Despite this apparent simplicity, there exists no orthogonal coordinate system in which the wave equation for the hexagonal cavity can be solved by separation of variables. This property of non-integrability is shared by wave equations whose classical (short-wavelength) limit exhibits chaos. However, ray paths in the hexagon display a degree of complexity that cannot be classified as chaotic, and hence the term pseudointegrability has been coined for these systems. The ray-wave duality in “billiards” of this type has to be addressed in order to explain how they can support whispering-gallery modes that emit at the corners.

In order to characterize the sample size, one can specify either the radius $`R`$ of the hexagon at the corner points or – more conveniently – the width over flats (WoF) satisfying the relation $`R=WoF/\sqrt{3}`$. The closed ray path underlying Fig. 6 is only one member of an infinite family of periodic orbits of the hexagon billiard that all have the same length, $`L=3\times WoF`$, as shown in Fig. 7. Long-lived cavity modes should be expected only if the corresponding rays satisfy the condition of TIR at the interface, $`\mathrm{sin}\chi >1/n`$, where $`\chi `$ is the angle of incidence with respect to the surface normal. This is true for the orbits of Fig. 7. In a naive ray approach one would furthermore obtain the spectrum of modes by requiring an integer number of half wavelengths to fit into $`L`$, leading to constructive interference on a round-trip. As we shall see shortly, this estimate is justified, even though a proper treatment of the ray-wave connection has to take into account that any given mode is in fact made up of a whole family of different ray paths. The ultimate breakdown of the ray model, however, is illustrated in Fig. 7 by the degenerate ray orbit hitting the corners where the classical laws of refraction and reflection become undefined.

### 3.2 Wave picture: spectral properties

Because the hexagonal faces are neither focussing nor defocussing, there is no obvious way of determining the weight that should be given to individual members of a ray family as depicted in Fig. 7, in order to predict the spatial structure of the resulting mode. Full solutions of Maxwell’s equations have therefore been carried out for the TM polarized modes of a dielectric hexagonal prism, using methods previously applied in nature ; gmachl . In anticipation of the experimental spectra to be discussed in section 4, attention here is focused on three different sample sizes, with WoF $`4.5\mu `$m, $`7.5\mu `$m and $`22\mu `$m. The aim is to understand the observed laser line spacings and the emission directionality. Comparison of the calculated and observed linewidths will not be attempted because the simulations do not take gain-narrowing into account.

In order first to verify that orbits of the type shown in Fig. 7 determine the characteristic mode spacing of these cavities, Fig. 8 shows light scattering spectra for different sample sizes in the vicinity of the experimental wavelengths. Intensity is plotted versus dimensionless wavenumber $`kR`$, where $`k=2\pi /\lambda `$. This is the natural scale for comparison with semiclassical predictions because modes differing by one node along a closed path should then be equally spaced, with a characteristic separation $`\mathrm{\Delta }(kR)_c=2\pi R/(nL)=2\pi /(3\sqrt{3}n)=0.825`$ independent of the sample size. The expected wavelength spacing of the modes (free spectral range $`FSR`$) is $`\mathrm{\Delta }\lambda =\lambda ^2\times \mathrm{\Delta }(kR)_c/(2\pi R)23`$ nm in (a) and $`\mathrm{\Delta }\lambda 11`$ nm in (b). For $`WoF=22\mu `$m, we obtain $`\mathrm{\Delta }\lambda 4.9`$ nm. Figure 8 indeed shows a series of resonant features with approximately the predicted wavevector spacing.

Each of the peaks marked in Fig. 8 (b) is in fact a multiplet, which is not resolved because the splittings of the individual modes comprising the multiplet are smaller than their passive linewidths. There is evidence for this because several of the peaks are very asymmetric and in particular exhibit a steep slope on one side. For an isolated resonance, the most general lineshape that could arise is the Fano function (of which the Lorentzian is a special case), which however does not yield satisfactory fits here.

To further expose the multiplet structure, we modeled deviations from the ideal hexagonal shape which could lead to narrower individual linewidths and increase the multiplet splitting. Shape perturbations were chosen that preserve the $`D_{6h}`$ point group symmetry and hence remove only “accidental” quasi-degeneracies. The actual perturbation that is present in the samples of Figs. 11 and 12 eluded experimental characterization, so that a model calculation can reproduce only generic features which are insensitive to the precise type of perturbation. One such feature is the average mode spacing after degeneracies have been lifted sufficiently.

Figure 9 (a) shows the spectrum of a rounded hexagon where the radius of curvature at the corners is $`\rho 0.9\lambda `$ (assuming $`\lambda 610`$ nm for definiteness). No qualitative difference to Fig. 8 (b) is seen, except that the resonant features have become somewhat narrower, thus enabling us to identify two distinct series of modes with caracteristic spacing $`\mathrm{\Delta }(kR)_c`$. This indicates that departures from sharp corners are not resolved in the wave equation when their scale is smaller than $`\lambda `$. A qualitatively different spectrum is observed in Fig. 9 (b) where $`\rho 3.7\lambda `$. Here, the perturbation reveals three well-separated, interpenetrating combs of modes, again with period $`\mathrm{\Delta }(kR)_c`$. There are $`21`$ distinct resonances in the wavelength interval of Fig. 9 (b), which translates to an average mode spacing of $`\mathrm{\Delta }\lambda 3.6`$ nm for a $`WoF=7.5\mu `$m resonator, well in agreement with the experiment; cf. Fig. 12.

In order to verify that no further modes will be revealed by other choices of deformation, an independent estimate of the average density of modes can be made based on semiclassical considerations noeckelunpublished :

$`{\displaystyle \frac{dN}{d(kR)}}`$ $`=`$ $`{\displaystyle \frac{n^2kR}{4}}`$ (1)
$`\times `$ $`\left[1{\displaystyle \frac{2}{\pi }}\left(\mathrm{arcsin}{\displaystyle \frac{1}{n}}+{\displaystyle \frac{1}{n}}\sqrt{1{\displaystyle \frac{1}{n^2}}}\right)\right]`$
Here, $`dN`$ is the number of modes in the interval $`d(kR)`$. The result is $`\frac{dN}{d(kR)}4.6`$, and hence we expect $`22`$ modes in the interval of Fig. 9 (b), again in good agreement with the actual count.

### 3.3 Wave picture: intensity profile

There is one class of quasi-degeneracies that is not removed by any of the perturbations in Fig. 9: their physical origin is time-reversal symmetry for the ray motion inside the cavity. Any of the periodic orbits in Fig. 7 can be traversed either clockwise or counterclockwise, and the same holds for more general ray paths. The different propagation directions can be linearly combined in various ways to obtain nearly-degenerate standing-wave patterns that differ only in their parity with respect to some of the crystal’s reflection axes. A minute splitting does exist because the non-integrability of the ray motion implies that the propagation direction itself is not a “good quantum number”, i.e. reversals of the sense of rotation are unlikely but not impossible in the wave equation. This is analogous to quantum tunneling and hence leads only to exponentially small splittings that can be neglected on the scale of the individual resonance linewidths DAV81 . These multiplets have been counted as one resonance in Eq. (1).

Following this reasoning, in Fig. 10 the traveling-wave patterns belonging to one of the resonances in Fig. 8 (a) and (b), respectively, is plotted. High-intensity ridges inside the resonator form a whispering-gallery-like pattern that decays from the interface into the cavity center. The number of ridges in the radial direction (perpendicular to a side face) provides an approximate analogue of a transverse mode order, however upon closer examination one sees that the number of ridges and nodal lines is not uniquely defined, in particular along a diameter joining opposite corners. The modes can therefore not be properly labeled by “good quantum numbers” characterizing the number of radial and azimuthal nodes – this is a direct consequence of the nonintegrability of the problem. The most significant difference to the whispering-gallery modes of a circular cavity is clearly the anisotropic emission. High intensity is seen to emanate predominantly from the corners and is directed almost parallel to an adjacent crystal facet. The overall emission pattern is very similar in both modes despite the large difference in size (or $`kR`$) between the two hexagons.

## 4 Laser properties

The microcrystals were pumped with 10 ns pulses from the 532 nm second harmonic of a Nd:YAG-laser delivered to the sample with an optical fiber. The emitted luminescence was collected with a $`20\times `$-microscope objective (collecting aperture 42) relaying the microlaser emission simultaneously to the spectrometer (cooled CCD-detector Oriel InstaSpecIV), and to the imaging system consisting of a cooled low noise CCD-camera (PCO SensiCam). In Fig. 11 the emission and lasing spectra of different pyridine 2-loaded compounds are shown. With increasing dye content the fluorescence emission maximum of regularly shaped crystals shifted from 645 nm to 665 nm; cf. Fig. 11a. In none of these rod-shaped crystals laser emission was observed. However, narrow laser emission peaks (observed linewidth of 0.3 nm given by spectrometer resolution) occured in most fascicled samples. Emission maxima in these fascicled samples were observed at wavelenghts up to 695 nm, and again, increasing dye concentration correlated with increasing redshift (cf. Figs. 11b and c). As already mentioned, together with increasing dye content we also notice an increasingly disarranged crystal morphology. The observed facts, disturbed morphology and red-shifted emission spectrum are consistent with the hypothesis of a host-guest interaction which increases with dye content. Essentially both, the pyridine 2 molecules and the AlPO4-5 framework carry a static dipole moment BEN83 ; MAR94 . Obviously the buildup of electrostatic energy in the crystal lattice has to be compensated by an increasing amount of stacking faults. On the other side, the mechanism of the redshift is not unequivocally identified, yet, but is probably related to the one discussed in FOE49 ; FOE51 .

The dye concentration in the rhodamine BE50-loaded AlPO4-5 samples was around 75 unit cells per dye molecule, corresponding to 0.5 wt%. Also with these samples the same correlation between the emission wavelength and dye concentration was observed; cf. also BOC98 . In contrast to the pyridine 2-loaded samples, the fluorescence emission was not completely polarized. The observed polarization contrast $`c_p=\frac{I_{}I_{}}{I_{}+I_{}}`$ was around 10%, indicating that in the average the Rh BE50 molecules are only weakly aligned parallel to the crystal $`c`$-axis.

Independent of the type of loading, in most microcrystals with $`WoF`$ 8 $`\mu `$m lasing was observed to occur on several sharp lines with instrument resolution limited width. A typical example is represented in Fig. 12. Note that the lines are not equally spaced. In fact, the free spectral range ($`FSR`$) of 11 nm corresponding to the resonator size is far above the observed line spacing of 3.2, 4.3 and 3.4 nm. This is in agreement with the theoretical model of paragraph 3.2, in which the average lasing mode spacing (after lifting the quasi-degeneracies in the ideal hexagon) was estimated to be $`\mathrm{\Delta }\lambda =`$ 3.6 nm. Also in agreement with the theoretical discussion are the emission regions where the laser light leaves the hexagonal resonators. Figure 13(left) shows the laser emission as bright spots. Clearly the emission is concentrated along the crystal edges. The complex emission distribution is compatible with the simultaneously recorded spectrum (cf. Fig. 12) which reveals multimode emission.

On the other hand, samples with smaller resonator ($`WoF`$ 4 $`\mu `$m), as e.g. the one shown in Fig. 11b emitted one single laser line. Therefore the emission is unadulterated by hole burning induced multimode beating and interference, and appears in the simple pattern shown in Fig 13(right), where two ca. 1 $`\mu `$m-spots ($``$ microscope resolution limit) mark the region of laser emission, which, again, is located on the crystal edges. Compared with larger samples, the ratio of the line peak to the underlying fluorescence shoulder of these small lasers is an order of magnitude higher (cf. Fig. 14).

While, as described above, the average linespacing of 3.6 nm observed in the sample of Fig. 12 is not compatible with the free spectral range of $`\mathrm{\Delta }\lambda =12`$ nm of the corresponding resonator, the 4.2 nm spacing of the 3 dominant peaks in the sample shown in Fig. 11c is in accord with the $`FSR`$ resulting from the 22-$`\mu `$m-WoF hexagonal resonator. The theoretical model for the $`22\mu `$m-WoF sample (cf. Eq. (1)) yields an average mode spacing of $`\mathrm{\Delta }\lambda `$ 0.5 nm which is close to the spectrometer resolution. This high spectral density helps to explain the large background in the lasing spectrum of Fig. 11: It appears likely that not all the individual lasing modes in this sample were resolved, and hence part of the shoulder on which the three peaks of curve c sit is probably made up of other lasing modes. Any microcavity effects such as enhanced $`\beta `$ factor (spontaneaous emission enhancement and suppression YAM96 ) are also suppressed by the larger density of modes in the large sample.

Figure 14 illustrates the differential efficiency behavior of a typical microlaser with $`WoF<10\mu `$m and one with $`WoF>10\mu `$m. Lasing threshold for the latter size samples was around 0.5 MW/cm2, regardless of the type of dye loading. On the other side, crystals of smaller size ($`WoF=4.5\mu `$m) from the same synthesis batch revealed a considerably smaller threshold (0.12 MW/cm2) and a factor of $`>7`$ larger differential gain. Wether this is a consequence of quantum size effects YAM96  will be clarified in progressing studies.

It is informative to compare the threshold of molecular sieve microlasers with vertical cavity surface emitting lasers (VCSELs). VCSELs with a size comparable to sample b in Fig. 11 exhibit threshold currents of ca. 1 mA, which corresponds to $`6.25\times 10^{15}`$ s-1 electrons. On the other hand, the threshold power density of 0.12 MW/cm2 incident on the molecular sieve laser surface of $`1\times 4.5\mu `$m (cf. Fig. 13) corresponds to a current of $`1.4\times 10^{16}`$ s-1 532-nm-photons, or a factor of 2.24 over the electron rate. As the pump radiation is not polarized but the molecular ensemble of the considered laser is aligned, only half of the pump photons actually contribute to the inversion. Thus, in terms of elementary (quantum) pump processes needed to reach lasing threshold the molecular sieve lasers are comparable to VCSELs.

## 5 Photostability

Photostability is a critical issue with dye lasers. We investigated samples exhibiting an undisturbed morphology, similar to the one shown in Fig. 1. The pyridine 2-loaded samples were irradiated with 10 Hz trains of 10 ns pulses of the 532 nm second harmonic of a Nd:YAG-laser and a power density of 5 MW/cm2. Figure 15 illustrates the dwindle of fluorescence activity of a pyridine 2-loaded AlPO4-5 sample under such bleaching irradiation. After a bleaching period of 140 seconds the exposure was interrupted for 18 minutes. Then the bleaching procedure was resumed. Apparently the fluorescence recovers during the intermission. If it is assumed that bleaching consists in breaking bonds of the dye molecules, then bond energies in the eV-range have to be considered. Even if the dye debris might remain encaged in their pores, spontaneous or thermally activated self healing of broken eV-bonds seems not very probable. One can therefore suppose that the recovery is due to diffusion of new, intact dye molecules into the bleached volume. Considering the stereometrically restricted possibilities inside the molecular sieve framework together with diffusion distances of several $`\mu `$m and the observed recovery time in the range of minutes, diffusion is more plausible than self healing.

As bleaching reduces the concentration of dye, a blueshift of the fluorescence is expected with increasing photobleaching BEN83 ; MAR94 . However, the 656-nm-fluorescence emission maximum of this sample is already at the shortest observed wavelength (cf. Fig. 11), corresponding to a low dye concentration, and consequently, to weak dipole interactions. Thus, the blueshift under these circumstances must be rather small. This explains the fact that we could not detect a measurable blueshift with these pyridine 2-loaded samples.

On the other hand, the rhodamine BE50-loaded samples under investigation contained dye at a concentration of around one Rh BE50 molecule per 75 unit cells, and therefore bleaching caused a detectable 4 nm shift of the fluorescence towards the blue (bleach irradiance 0.5 MW/cm2). Observing the laser emission spectrum while bleaching the samples, a further consequence of the blueshift was revealed: Blueshift of the fluorescence reduces the overlap of the fluorescence band with the absorption spectrum, and as a result laser modes at lower wavelengths will suffer less losses with increasing bleaching. This is documented in Fig. 16, where the intensity of mode b with the shortest oscillating wavelength increases, while longer-wavelength-modes a and c decrease during the bleach procedure. At the same time a 0.2 nm blueshift of the oscillation wavelength was detected. We attribute this to a weak decrease of the refractive index of the resonator material due to the smaller polarizability of the dye debris. In contrast to the pyridine 2 samples, however, recovery of the fluorescence was not detected. As the Rh 50BE molecules are considerably larger than pyridine 2 molecules their mobility in the molecular sieve framework is severly hampered. So, diffusion of intact molecules into the bleached volume occurs – if ever – on larger timescales than minutes.

## 6 Conclusion

We have reported about a new form of microlasers based on nanoporous molecular sieves containing embedded dyes. Size- and shape-dependent laser properties were observed, in agreement with theoretical predictions: Larger hexagonal crystals ($`WoF10\mu `$m) revealed multiline laser emission, while the smaller ones ($`WoF5\mu `$m) oscillate on one single line. The laser threshold power density of these small lasers is approximately a factor of 3 lower than the threshold of $`WoF10\mu `$m–lasers, and their differential efficiency is almost an order of magnitude larger. Although these properties did not depend on the type of embedded dye molecules, the photostability seems to be affected by the size of the molecules. Molecules which fit into the pores, such as pyridine 2, keep the ability to diffuse in the pore framework of the molecular sieve. Therefore photobleached molecules can be replaced by intact ones diffusing into the luminescing volume.

(Acknowledgement: This work was partially funded by the Deutsche Forschungsgemeinschaft)


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# Spin versus Lattice Polaron: Prediction for Electron-Doped CaMnO3

## I Introduction

CaMnO3 is a bi-partite (G-type) antiferromagnetic(AF) insulator with Néel temperature $`T_N`$=125K, and almost perfect cubic perovskite crystal structure. There is not a large literature on this material. It deserves attention as a particularly simple case of an AF insulator which can be electron-doped. The $`(T,x)`$ phase diagram  of the Ca1-xLaxMnO3 series has attracted attention because of the fascinating interplay of spin order, orbital order, and metallic versus insulating transport. “Colossal magnetoresistance” (CMR) occuring at concentration $`x0.65`$ and $`T250`$ K is the most dramatic manifestation . For small $`x`$, magnetization and conductivity measurements  suggest local ferromagnetic(FM) regions or “spin polarons” in the range $`0.02<x<0.06`$. In this paper we use a model for pure CaMnO3, the $`x=0`$ end member, and predict its behavior under light doping, $`x1`$. We keep $`T`$ equal to 0 and neglect lattice zero-point energy, but all other degrees of freedom are allowed and interact in interesting ways.

Our main question is, what is the ground state of an excess electron in CaMnO3? The answer to this question will also apply to lightly doped CaMnO3 provided the doped state is homogeneous. Our model has four parameters. (1) The bandwidth parameter $`t`$ governs the effective Mn $`E_g`$ electron hopping between Mn3+ and Mn4+ through the intervening oxygen. The spins of the two Mn ions must be parallel as in the usual “double exchange” model. (2) The magnetic exchange parameter $`J`$ couples spins of first-neighbor Mn ions, due to virtual hopping of $`T_{2g}`$ electrons. (3) The electron-phonon coupling constant $`g`$ describes interactions between Mn $`E_g`$ orbitals and the 6 nearest oxygen atoms. (4) Oxygen displacements $`u`$ are opposed by the restoring force $`Ku`$, where $`\omega =\sqrt{K/M}`$ is an Einstein frequency assigned to oxygen vibrations along the bonds. There are two important dimensionless parameters. Spin polarons  are controlled by the ratio $`\beta =t/JS^2`$. Jahn-Teller (JT) lattice polarons  are controlled by the parameter $`\mathrm{\Gamma }=g^2/Kt`$ . Balancing these competing effects, we find the most favorable local FM spin arrangement, lattice distortion and electron wavefunction. As doping increases, we predict a transition from polaronic insulator to FM metal.

## II Model Hamiltonian

The Mn4+ ion in CaMnO3 has configuration $`3d^3`$, i.e., the three spin-aligned $`T_{2g}`$ states $`(xy,yz,zx)`$ are filled with electrons, while the two spin-aligned $`E_g`$ states $`(\psi _2=(x^2y^2)/\sqrt{3},\psi _3=3z^2r^2)`$ are empty and lie above by the crystal field splitting. The empty opposite-spin $`T_{2g}`$ states are split to even higher energy by the Hund term $`J_H`$. Light electron doping puts carriers into the doubly-degenerate $`E_g`$ level. Hopping of $`(dd\pi )`$-type occurs from $`T_{2g}`$ to $`T_{2g}`$, and of $`(dd\sigma )`$-type from $`E_g`$ to $`E_g`$, but no $`E_g`$ to $`T_{2g}`$ hopping matrix element exists because of the simple cubic structure. Virtual $`T_{2g}`$ hopping  (at the cost of Hubbard energy $`U`$) gains delocalization energy if adjacent spins are antiparallel. This gives an $`S=3/2`$ antiferromagnetic Heisenberg Hamiltonian with exchange coupling $`J=2(dd\pi )^2/U`$ , $`U`$ being large compared with $`(dd\pi )`$ , and agrees with the experimentally observed magnetic structure of pure CaMnO3. The ground state has $``$ spins on the A sublattice (when $`\mathrm{exp}(i\stackrel{}{Q}\stackrel{}{l})=1`$, where $`\stackrel{}{l}`$ labels the Mn sites), and $``$ spins on the B sublattice (when $`\mathrm{exp}(i\stackrel{}{Q}\stackrel{}{l})=1`$) with $`\stackrel{}{Q}=(\pi ,\pi ,\pi )`$.

Ignoring for now the electron-phonon terms, the Hamiltonian for an excess electron is $`=_t+_J`$. The first term contains hopping of Mn $`E_g`$ electrons to nearest neighbors,

$`_t`$ $`=`$ $`t{\displaystyle \underset{l,\pm }{}}[S(\stackrel{}{l},\stackrel{}{l}\pm \widehat{z})c_3^{}(\stackrel{}{l}\pm \widehat{z})c_3(\stackrel{}{l})`$ (1)
$`+`$ $`\text{rotations to }\widehat{x}\text{,}\widehat{y}\text{ directions}],`$ (2)
$$S(1,2)=\mathrm{cos}\frac{\theta _1}{2}\mathrm{cos}\frac{\theta _2}{2}+\mathrm{sin}\frac{\theta _1}{2}\mathrm{sin}\frac{\theta _2}{2}e^{i(\varphi _1\varphi _2)}$$
(3)
Here $`c_3(\stackrel{}{l})`$ destroys an electron state $`\psi _3(\stackrel{}{r}\stackrel{}{l})`$ on the Mn atom at $`\stackrel{}{l}`$; $`\stackrel{}{l}\pm \widehat{z}`$ labels the Mn neighbors above and below the one at site $`\stackrel{}{l}`$; and $`t`$ is the $`(dd\sigma )`$ integral from Slater-Koster two-center theory . We use a value $`t=0.75`$ eV obtained from fitting the band structure of CaMnO3 (see Sec. III). The factor $`S(1,2)`$ comes from locally rotating the axis of spin quantization for the $`i^{\mathrm{th}}E_g`$ electron into the direction $`(\theta _i,\varphi _i)`$ of the $`i^{\mathrm{th}}S=3/2`$ core spin, treating the angles $`(\theta _i,\varphi _i)`$ as classical parameters, and discarding from the Hilbert space the state with spin opposite to the core spin (i.e. assuming $`J_H\mathrm{}`$ ). In this paper, we usually take the spins to be perfectly ordered at $`T=0`$, that is, $`\theta =\theta _1\theta _2`$ equals 0 or $`\pi `$, corresponding to $`S(1,2)`$ equal to 1 or 0 for FM or AF oriented neighbors. We will also consider uniformly canted states where a relative angle $`\theta =\pi \theta _0`$ occurs, with $`\varphi `$=constant, so that $`S`$ takes the value $`\mathrm{sin}(\theta _0/2)`$. These spin orientations are shown in Fig. 1.

The rotation of $`\psi _3`$ to the $`\widehat{x}`$ axis is $`(\psi _3+\sqrt{3}\psi _2)/2=3x^2r^2`$, and to the $`\widehat{y}`$ axis it is $`(\psi _3\sqrt{3}\psi _2)/2=3y^2r^2`$. Using these, we rewrite $`_t`$ in the usual orthonormal basis ($`\psi _2,\psi _3`$),

$$_t=t\underset{l,\delta =x,y,z}{}\left(\begin{array}{cc}c_2^{}(\stackrel{}{l})& c_3^{}(\stackrel{}{l})\end{array}\right)𝖳_\delta \left(\begin{array}{c}c_2(\stackrel{}{l}\pm \widehat{\delta })\\ c_3(\stackrel{}{l}\pm \widehat{\delta })\end{array}\right),$$
(4)
where it is understood that the hopping only operates between parallel spin Mn atoms. The hopping matrices are

$$𝖳_x=\left(\begin{array}{cc}\frac{3}{4}& \frac{\sqrt{3}}{4}\\ \frac{\sqrt{3}}{4}& \frac{1}{4}\end{array}\right),𝖳_y=\left(\begin{array}{cc}\frac{3}{4}& \frac{\sqrt{3}}{4}\\ \frac{\sqrt{3}}{4}& \frac{1}{4}\end{array}\right),𝖳_z=\left(\begin{array}{cc}0& 0\\ 0& 1\end{array}\right).$$
(5)
The $`_J`$ term is the AF nearest neighbor $`T_{2g}`$ exchange:

$$_J=\underset{<l,l^{}>}{}J\stackrel{}{S}(\stackrel{}{l})\stackrel{}{S}(\stackrel{}{l}^{})$$
(6)
The exchange coupling $`J`$ is can be estimated from Mean Field theory (we use a quantum treatment for spin 3/2; FM and AFM answers are equal) to be $`JS^2=3.23`$ meV, using the measured Néel temperature $`T_\mathrm{N}=125`$ K . However, for a given coupling $`J`$, a more accurate estimate from susceptibility expansions reduces the $`T_\mathrm{C}`$ of the Heisenberg ferromagnet

$$\frac{T_\mathrm{C}}{T_{\mathrm{C}(\mathrm{MF})}}=\frac{\frac{5}{96}(z1)[11S(S+1)1]}{\frac{2}{3}zS(S+1)},$$
(7)
where $`z=6`$ is the number of nearest neighbors. For a Heisenberg antiferromagnet it is estimated that $`T_N`$ is slightly higher,

$$\frac{T_\mathrm{N}}{T_\mathrm{C}}1+\frac{0.63}{zS(S+1)}.$$
(8)
Making these corrections, the coupling is found to be $`JS^2=4.74`$ meV, giving $`t/JS^2`$=158, with probable uncertainty of 10%. The phonon parts of the Hamiltonian are given in Sec. V.

## III uniform solutions

First consider the hypothetical case of a uniform FM spin order. Then a doped-in electron could hop without paying a Hund penalty, and extended Bloch states would form with wavefunctions

$$\mathrm{\Psi }_k=d_2\frac{1}{\sqrt{N}}\underset{l}{}e^{i\stackrel{}{k}\stackrel{}{l}}\psi _2(\stackrel{}{l})+d_3\frac{1}{\sqrt{N}}\underset{l}{}e^{i\stackrel{}{k}\stackrel{}{l}}\psi _3(\stackrel{}{l}),$$
(9)
where $`d_2,d_3`$ are coefficients. Diagonalizing Eq.(4), the resulting energy eigenvalue, taking into consideration that $`t`$ is negative, is

$`{\displaystyle \frac{E(\stackrel{}{k})}{|t|}}`$ $`=`$ $`\mathrm{cos}k_x\mathrm{cos}k_y\mathrm{cos}k_z`$ (12)
$`(\mathrm{cos}^2k_x+\mathrm{cos}^2k_y+\mathrm{cos}^2k_z`$
$`\mathrm{cos}k_x\mathrm{cos}k_y\mathrm{cos}k_y\mathrm{cos}k_z\mathrm{cos}k_z\mathrm{cos}k_x)^{1/2}.`$
At $`\mathrm{cos}k_x=\mathrm{cos}k_y=\mathrm{cos}k_z=1`$, the energy is minimum, $`E(\stackrel{}{k}=0)=3|t|`$, the state being doubly degenerate. Although the actual spin arrangement is not FM, the result $`|3t|`$ sets a useful scale for the maximal energy gain from electron delocalization. Also, the dispersion relation (LABEL:eq:Ek) can be fitted to a FM CaMnO3 majority-spin band structure calculated in density-functional theory , determining the hopping energy $`t=0.75`$ eV.

For light doping, the magnetic energy Eqn.(6) of antiferromagnetic order ($`zJNS^2/2`$ for classical spins; $`N`$ is the number of Mn ions) is much larger than hopping energy. As discussed by deGennes , the best uniform solution (for a one-band model) is a compromise where antiferromagnetic spins cant uniformly toward FM solutions. Start from the Néel AF structure and let all spins tilt towards the $`\widehat{x}`$ direction with angle $`\theta /2`$, as shown in Fig. 1. This costs magnetic energy $`\mathrm{\Delta }E_J=zNJS^2(1\mathrm{cos}\theta )/2`$. A doped-in electron can now delocalize, reducing its energy by $`3|t|\mathrm{sin}(\theta /2)`$. For small doping $`x=n/N1`$, the total hopping energy is $`\mathrm{\Delta }E_t=3n|t|\mathrm{sin}(\theta /2)`$. Therefore when $`\mathrm{sin}(\theta /2)=x|t|/4JS^2`$, the total energy $`\mathrm{\Delta }E=\mathrm{\Delta }E_J+\mathrm{\Delta }E_t`$ is minimum, $`3Nx^2t^2/8JS^2`$. From this estimate, the system cants all the way to FM when the optimal $`\theta `$ equals $`\pi `$, which occurs at $`x=4JS^2/|t|0.025`$.

Because the doubly-degenerate $`E_g`$ electrons hop anisotropically, a better canted solution exists. Let all spins with $`\mathrm{exp}(i\stackrel{}{K}\stackrel{}{ł})=1`$ ($`\stackrel{}{K}`$ is $`(0,\pi ,\pi )`$) tilt towards $`+\widehat{x}`$ and all spins with $`\mathrm{exp}(i\stackrel{}{K}\stackrel{}{ł})=1`$ tilt towards $`\widehat{x}`$ with angle $`\theta /2`$, as shown in Fig. 1. The magnetic energy cost is reduced to $`\mathrm{\Delta }E_J=zNJS^2(1\mathrm{cos}\theta )/6`$, but the delocalizaton energy lowering is also reduced to $`\mathrm{\Delta }E_t=2n|t|\mathrm{sin}(\theta /2)`$. This type of canting terminates in C-type antiferromagnetism when $`x=2JS^2/t`$, as shown in Fig. 1. Fig. 2 summarizes our results for the energies of uniform solutions versus $`x`$.

## IV Pure Spin Polaron Effect

Experimentally, CaMnO3 is insulating at small doping $`x`$. This rules out uniform solutions with electrons doped into delocalized states. The simplest picture is that each doped electron is localized on one Mn site, creating a local Mn3+ with spin $`S=2`$ in an AF background, for a spin excess of 1/2. This does not agree with the measured saturated magnetization , which has been interpreted in terms of local spin flipping (net excess spin of 2) in the region $`0.02<x<0.08`$. Local spin flipping leads to local FM regions (called spin polarons) around doping centers, allowing the doped electron to gain delocalization energy. In this section we discuss candidate localized ground states of a single $`E_g`$ electron, using the same Hamiltonian $`=_t+_J`$.

First we make a continuum (effective mass) approximation in the spirit of Nagaev . Inside the local FM region, electrons hop like free electrons with inverse band mass $`1/m^{}=(a/\mathrm{})^2|t|`$ given by Eqn.(LABEL:eq:Ek), with $`a`$ the perovskite lattice constant, $`a3.73\AA `$. This electron sits in a spherical well with infinite walls at radius $`R`$, whose depth is $`3|t|`$. G-type antiferromagnetism resumes for $`r>R`$. The ground state energy of the electron in this polarized region is then

$$\mathrm{\Delta }E_t=|t|(3+\frac{\pi ^2a^2}{2R^2}),$$
(14)
where the second term is the zero-point energy in the well. The magnetic energy cost from spin-canting is

$$\mathrm{\Delta }E_J=zJS^2(4\pi R^3/3a^3),$$
(15)
where the last factor is the number of Mn atoms in the cluster. Optimizing $`\mathrm{\Delta }E=\mathrm{\Delta }E_t+\mathrm{\Delta }E_J`$ over R, the optimal size cluster has a number of Mn atoms inside the sphere equal to

$$\frac{4}{3}\pi \left(\frac{R}{a}\right)^3=\frac{4}{3}\pi \left(\frac{\pi |t|}{4zJS^2}\right)^{3/5}26.$$
(16)
This is close to the optimum 25-site symmetric cluster which we will find by exact diagonalization and show in Table I. However, we will also find a smaller asymmetric cluster of lower energy.

It is interesting that continuum theory gives a lower energy if the region $`r<R`$ is canted rather than fully FM. The A sublattice is fixed for all $`r`$, but the B sublattice is tilted toward the A sublattice by angle $`\theta `$ for $`r<R`$. Then the optimum tilting angle is 180 (FM) for $`\beta =t/JS^2>\beta _c=(7\pi ^2/18)^{5/2}4z/\pi 220`$, while for smaller $`\beta `$, the optimal tilting angle is $`\mathrm{sin}(\theta /2)=\beta /\beta _c`$. Our estimated value is $`\beta 158`$, which gives $`\beta /\beta _c0.72`$. So the spins inside radius $`R`$ are approximately 90 apart, and the optimum cluster increases to 31.

Now we repeat the calculation using the true discrete Hamiltonian. First consider flipping only one spin. In this way, the spin-flipped Mn (the central site), along with its 6 nearest neighbors, form a 7-site cluster with all 7 spins parallel. The cluster is invariant under transformations of the point group $`O_h`$. If the central Mn spin is kept unflipped, but instead the spins of those 6 nearest neighbors are flipped, a 25-site $`O_h`$-symmetric cluster is formed. Similar steps can be taken to obtain larger and larger symmetric clusters. We will not look at candidate states with canted spins except for one special case to be mentioned later.

Each spin flip costs magnetic energy $`6\times 2JS^2`$. Since spins are parallel inside the cluster, the electron can hop among the $`E_g`$ orbitals of all the spin-aligned Mn ions, with a corresponding energy lowering from delocalization. Table I shows numerical values of ground state energy found by exact diagonalization of $`2M\times 2M`$ Hamiltonian matrices for symmetric clusters of $`M`$ Mn atoms, ranging in size from $`M`$=1 to 63. The ground states are all doubly degenerate (Eg representation) because of the $`O_h`$ symmetry of the cluster.

Asymmetric clusters are also possible. If we flip one spin at site $`\stackrel{}{l}`$ and another one at site $`\stackrel{}{l}+\widehat{x}+\widehat{y}`$, a 12-site cluster is formed. Starting from this 12-site cluster, there are four different ways to create a larger cluster with one more flipped spin, as shown in Fig. 3. Other possibilities are less closely packed, such as the 13-site cluster shown in the figure, and other 3-spin-flipped cases not shown here. The ground state energy of these examples are calculated, as shown in Table II. For our chosen values of $`t`$ and $`JS^2`$, the most favorable spin polaron is an asymmetric 17-site cluster with three flipped spins.

There are many possible variations with inhomogeneously canted spins, of which we considered only one, a 25-site cluster with the 7 inner atoms canted rather than ferromagnetically aligned with the outer 18 atoms. This interpolates between the 7 and the 25 atom cluster. Without canting, the 7 and 25 atom cluster become equal in energy for the value $`|t|/JS^2100`$, smaller than our preferred value of 158. It turned out that in the range $`94<|t|/JS^2<104`$, the locally canted state was lower in energy than either the 7 or the 25 atom pure ferromagnetic cluster.

## V Lattice Polaron Effect

The degenerate ground state, found in the previous section for symmetrical spin polarons, is Jahn-Teller (JT) unstable. We now add to our Hamiltonian lattice distortions, controlled by the electron-phonon interaction. The only lattice degrees of freedom included are oxygen motions along the bonds to the nearest two Mn ions. If an oxygen moves along this bond a distance $`u`$, it gets closer to one Mn atom and farther from another. This will raise by $`gu`$ (for the closer Mn) or lower by $`gu`$ (for the farther Mn) the energy of any occupied Mn $`E_g`$ state of the type which points toward the oxygen (that is, the $`3z^2r^2`$ state if oxygen motion in the $`\widehat{z}`$-direction is considered.) We use adiabatic approximation (oxygen mass $`\mathrm{}`$) and treat the oxygen distortions as classical parameters. Each Mn ion is surrounded by six oxygens whose distortion amplitudes $`(u_\delta (\stackrel{}{l}\pm \widehat{\delta }/2),\widehat{\delta }=\widehat{x},\widehat{y},\widehat{z})`$ form basis vectors for a representation of $`O_h`$, namely, $`a_{1g}e_gt_{1u}`$. The vector representation $`t_{1u}`$ contains the distortions $`u_z(\stackrel{}{l}+\widehat{z}/2)+u_z(\stackrel{}{l}\widehat{z}/2)`$, etc. The remaining 3 degrees of freedom $`(Q_z=u_z(\stackrel{}{l}+\widehat{z}/2)u_z(\stackrel{}{l}\widehat{z}/2),etc.)`$ form basis vectors of $`a_{1g}(Q_1=(Q_x+Q_y+Q_z)/\sqrt{6})`$ and $`e_g(Q_2=(Q_xQ_y)/2,Q_3=(2Q_zQ_xQ_y)/\sqrt{12})`$, in Van Vleck notation. The oxygen distortions are limited by a harmonic restoring force, e.g., $`Ku_z(\stackrel{}{l}\pm \widehat{z}/2)`$.

The lattice elastic energy and electron-phonon interaction terms of the Hamiltonian are

$`_\mathrm{L}`$ $`=`$ $`{\displaystyle \frac{K}{2}}{\displaystyle \underset{l}{}}[u_x(\stackrel{}{l}+{\displaystyle \frac{1}{2}}\widehat{x})^2+u_y(\stackrel{}{l}+{\displaystyle \frac{1}{2}}\widehat{y})^2+u_z(\stackrel{}{l}+{\displaystyle \frac{1}{2}}\widehat{z})^2],`$ (17)
$`_{\mathrm{ep}}`$ $`=`$ $`{\displaystyle \frac{4g}{\sqrt{3}}}{\displaystyle \underset{l}{}}[c_z^{}(\stackrel{}{l})c_z(\stackrel{}{l})Q_z(\stackrel{}{l})`$ (20)
$`+\text{rotations to }\widehat{x}\text{}\widehat{y}\text{ directions}].`$
$`_{\mathrm{ep}}`$ can be split into two parts, JT and “breathing”:

$$_{\mathrm{ep}}=_{\mathrm{JT}}+_{\mathrm{br}}$$
(21)
where, in Van Vleck notation,

$`_{\mathrm{JT}}`$ $`=`$ $`2g{\displaystyle \underset{l}{}}(\begin{array}{cc}c_2^{}(\stackrel{}{l})& c_3^{}(\stackrel{}{l})\end{array})\left(\begin{array}{cc}Q_3(\stackrel{}{l})& Q_2(\stackrel{}{l})\\ Q_2(\stackrel{}{l})& Q_3(\stackrel{}{l})\end{array}\right)\left(\begin{array}{c}c_2(\stackrel{}{l})\\ c_3(\stackrel{}{l})\end{array}\right)`$ (27)
$`_{\mathrm{br}}`$ $`=`$ $`2\sqrt{2}g{\displaystyle \underset{l}{}}Q_1(\stackrel{}{l})\left(c_2^{}(\stackrel{}{l})c_2(\stackrel{}{l})+c_3^{}(\stackrel{}{l})c_3(\stackrel{}{l})\right).`$ (28)
The vector distortions ($`t_{1u}`$) do not couple to $`E_g`$ electron states and therefore do not appear.

A simple case shows how $`_{\mathrm{JT}}`$ splits energy degeneracy. Suppose a doped electron is localized at a single Mn site, with no hopping or spin flipping considered. The two $`E_g`$ states at that Mn are the only degrees of freedom for the electron and are originally degenerate. When the six surrounding oxygen distortions are considered, the degeneracy is lifted in $`_{\mathrm{JT}}`$:

$`_{\mathrm{JT}}`$ $`=`$ $`2g(\begin{array}{cc}c_2^{}& c_3^{}\end{array})\left(\begin{array}{cc}Q_3& Q_2\\ Q_2& Q_3\end{array}\right)\left(\begin{array}{c}c_2\\ c_3\end{array}\right)`$ (34)
$`=`$ $`2g\left(\begin{array}{cc}\alpha ^{}& \beta ^{}\end{array}\right)\left(\begin{array}{cc}Q& 0\\ 0& Q\end{array}\right)\left(\begin{array}{c}\alpha \\ \beta \end{array}\right)`$ (40)
where

$`\left(\begin{array}{c}\alpha ^{}\\ \beta ^{}\end{array}\right)=\left(\begin{array}{cc}\mathrm{cos}\frac{\varphi }{2}& \mathrm{sin}\frac{\varphi }{2}\\ \mathrm{sin}\frac{\varphi }{2}& \mathrm{cos}\frac{\varphi }{2}\end{array}\right)\left(\begin{array}{c}c_2^{}\\ c_3^{}\end{array}\right)`$

and $`(Q_2,Q_3)=Q(\mathrm{sin}\varphi ,\mathrm{cos}\varphi )`$. The change in energy due to $`_{\mathrm{JT}}+_{\mathrm{br}}+_\mathrm{L}`$ is $`\mathrm{\Delta }E=2\sqrt{2}gQ_1\pm 2gQ+12(Q_1^2+Q^2)/2`$. The energy splitting $`\pm 2gQ`$ comes only from the JT term. The optimal distortions are $`Q_1=4\sqrt{2}g/K`$ and $`Q=4g/K`$, which give the maximum energy lowering of ground state $`\mathrm{\Delta }E=6g^2/K`$.

The angle $`\varphi `$ does not enter $`\mathrm{\Delta }E`$. This continuous degeneracy can be lifted either by adding kinetic energy and quantization of lattice degrees of freedom (dynamic JT effect), or else by introducing higher order anharmonic terms in $`_{\mathrm{ep}}`$ . However, later in the discussion of the 7-site cluster, we shall show how this continuous degeneracy is naturally removed by the increase of electronic and lattice degrees of freedom.

It is interesting to consider what would happen if spins were ferromagnetically ordered, so that magnetism does not assist localization. Then polaron formation can only occur through lattice distortion and is prohibited when the delocalization energy per electron is larger than the polaron energy, i.e., when $`\mathrm{\Gamma }=g^2/K|t|`$ is less than a critical value close to 0.5. We believe that $`\mathrm{\Gamma }`$ is close to 0.25, so that in the hypothetical ferromagnetic case, polarons would not form. Antiferromagnetic confinement is needed before a lattice polaron effect occurs. LaMnO3 is different in this respect; its cooperative Jahn-Teller ground state makes polaron formation easier .

## VI The 7-site cluster: Spin and Lattice Polaron

With the full Hamiltonian considered, the 7-site cluster turns out to be the most important one, as shown later in this section. Only a single spin is flipped. Inhomogeneous canting will not be favored for this state. By understanding its ground state algebraically, we learn several interesting aspects of the influence of $`_{\mathrm{ep}}`$ in the Hamiltonian. The dimensionless parameter $`\mathrm{\Gamma }g^2/Kt`$ characterizing the strength of electron-phonon coupling has a value near 0.25 for LaMnO3, and we assume that the value for for CaMnO3 is similar, i.e. $`0.20<\mathrm{\Gamma }<0.30`$. We will measure energies in units of $`|t|`$, using dimensionless lattice variables $`Q^{}\sqrt{K/|t|}Q`$. The prime in $`Q^{}`$ is suppressed from here on.

To study the ground state of a single electron in the 7-site cluster, a 14-dimensional Hilbert space is used, consisting of atomic $`E_g`$ orbitals from each of the 7 Mn atoms. Later when we turn on $`_{\mathrm{ep}}`$, we will find that for $`\mathrm{\Gamma }`$ small, fewer than 14 basis functions are needed for the ground state calculation. The 14-dimensional space can be decomposed into 7 irreducible representations of point group $`O_h`$, namely, $`A_{1g}A_{2g}T_{1u}T_{2u}3E_g`$. When lattice distortions are absent $`(\mathrm{\Gamma }=0,_{\mathrm{ep}}=_\mathrm{L}=0)`$, these functions diagonalize the 14-dimensional $`_t`$. The 3 $`E_g`$-type basis functions $`(\psi _2^+,\psi _3^+)`$, $`(\psi _2^0,\psi _3^0)`$ and $`(\psi _2^{},\psi _3^{})`$ are degenerate separately with eigenvalues $`+\sqrt{3}|t|`$, $`0`$, and $`\sqrt{3}|t|`$. These 6 states, along with the $`A_{1g}`$ state (with eigenvalue 0), will be the main states of interest when $`\mathrm{\Gamma }0`$. All other states stay absent as long as $`\mathrm{\Gamma }`$ is small.

When $`\mathrm{\Gamma }0`$, $`_{\mathrm{ep}}`$ and $`_\mathrm{L}`$ are turned on. Amplitudes of lattice distortions appear linearly in the matrix representation of $`_{\mathrm{ep}}`$, and quadratically in that of $`_\mathrm{L}`$. Since these lattice distortions are of order $`\sqrt{\mathrm{\Gamma }}`$ when $`\mathrm{\Gamma }1`$, $`_{\mathrm{ep}}`$ and $`_\mathrm{L}`$ can be treated as perturbations to $`_t`$ . In the following, all lattice distortion modes will be introduced. Then second order perturbation of the original ground states $`(\psi _2^{},\psi _3^{})`$ can be expressed in terms of these modes and shows that most of these modes do not participate in the ground state lattice distortion. This will in turn eliminate the need for considering electron states of symmetries which couple to the absent modes only. Finally, from the form of the perturbed ground state energy, the pattern of its optimized lattice distortion will be derived and compared to the exact numerical result.

There are 36 oxygens adjacent to one or more Mn atoms in the 7-atom cluster, so there are 36 distortion parameters in $`_{\mathrm{ep}}`$. These can be organized into sets of basis vectors for irreducible representations of the point group $`O_h`$, namely, $`3a_{1g}a_{2g}5t_{1\mathrm{u}}3t_{2\mathrm{u}}4e_g`$. The $`a_{1g}`$-type modes are denoted as $`(q_{i1}`$, where $`i=1,2,3)`$, and the $`e_g`$-type modes are denoted as $`(q_{i2},q_{i3})`$, where $`i=1,2,3,4`$. The matrix elements of $`_{\mathrm{ep}}`$ can be reexpressed in terms of these modes, and $`_\mathrm{L}`$ is simply $`_{\mathrm{modes}}q_{\mathrm{modes}}^2/2`$.

Second order perturbation theory shows that for small $`\mathrm{\Gamma }`$, many of these modes appear only quadratically with positive coefficients and hence should be optimized to $`0`$. For larger $`\mathrm{\Gamma }`$, these coefficients start to turn negative, and the corresponding distortions start to develop. The critical values are $`\mathrm{\Gamma }=0.443`$ for the appearance of the $`t_{1u}`$ and $`q_{43}`$ distortion, $`\mathrm{\Gamma }=1.30`$ for $`t_{2u}`$, $`\mathrm{\Gamma }=0.819`$ for $`a_{2g}`$ and $`q_{42}`$. It will thus happen that as $`\mathrm{\Gamma }`$ increases, the symmetry of the ground state electron wavefunction and lattice distortion pattern is gradually lowered by the successive appearance of these distortions.

We therefore ignore the above modes for the actual range $`\mathrm{\Gamma }0.25\pm 0.05`$. This eliminates the presence of electron states of $`A_{2g}`$, $`T_{1u}`$ and $`T_{2u}`$ symmetry. The remaining modes are 3 sets of $`(q_{i1},q_{i2},q_{i3})`$, with $`i=1,2,3`$, of the inner, intermediate and outer oxygen layers, respectively. Degenerate first-order perturbation theory for $`(\psi _2^{},\psi _3^{})`$ shows that the ground state energy of $`_t`$ splits into

$`{\displaystyle \frac{E^{(1)}}{\left|t\right|}}`$ $`=`$ $`\sqrt{3}\sqrt{\mathrm{\Gamma }}(\sqrt{2}Q_1\sqrt{Q_2^2+Q_3^2})`$ (41)
$`Q_1`$ $``$ $`{\displaystyle \frac{1}{3}}q_{11}+{\displaystyle \frac{1}{6}}q_{21}+{\displaystyle \frac{1}{12}}q_{31},`$ (42)
$`Q_2`$ $``$ $`{\displaystyle \frac{1}{3}}q_{12}+{\displaystyle \frac{1}{6}}q_{22}+{\displaystyle \frac{1}{12}}q_{31},`$ (43)
$`Q_3`$ $``$ $`{\displaystyle \frac{1}{3}}q_{13}+{\displaystyle \frac{1}{6}}q_{23}+{\displaystyle \frac{1}{12}}q_{33}.`$ (44)
Thus at first order, there is still a continuous degeneracy, in the sense that the energy JT splitting depends only on $`Q\sqrt{Q_2^2+Q_3^2}`$, not on $`\varphi \mathrm{tan}^1(Q_3/Q_2)`$.

To include 2nd order perturbations, for simplicity, we treat analytically only the distortion modes from the inner oxygen layer, $`(q_{11},q_{12},q_{13})`$. The number of related electronic states is now reduced to 5, namely, they are $`(A_{1g},\psi _2^+,\psi _3^+)`$ and $`(\psi _2^{},\psi _3^{})`$. In this 5-dimensional subspace, the Schrödinger equation to be solved can be expressed as follows (not including $`_\mathrm{L}`$, which is always proportional to the identity matrix):

$$\left(\begin{array}{cc}_t^{II}+_{\mathrm{ep}}^{II}E& h_{\mathrm{ep}}\\ h_{\mathrm{ep}}^T& _t^I+_{\mathrm{ep}}^IE\end{array}\right)\left(\begin{array}{c}\mathrm{\Psi }^{II}\\ \mathrm{\Psi }^I\end{array}\right)=0$$
(45)
where $`\mathrm{\Psi }^I(\psi _2^{},\psi _3^{})`$, $`\mathrm{\Psi }^{II}(A_{1g},\psi _2^+,\psi _3^+)`$. We obtain an effective Hamiltonian $`_{\mathrm{eff}}=_t^I+_{\mathrm{ep}}^Ih_{\mathrm{ep}}^T(_t^{II}+_{\mathrm{ep}}^{II}E)^1h_{\mathrm{ep}}`$ for $`\mathrm{\Psi }^I`$. Since $`E`$ should be very close to $`\sqrt{3}|t|`$ for small perturbation, we take $`E`$ as $`\sqrt{3}|t|\times \mathrm{𝟏}_{(3\times 3)}`$ and ignore $`_{\mathrm{ep}}^{II}`$ in the denominator. The $`_{\mathrm{eff}}`$ obtained this way shows that the degeneracy of $`(\psi _2^{},\psi _3^{})`$ is now lifted to become (including $`_\mathrm{L}`$)

$`{\displaystyle \frac{E^{(2)}}{\left|t\right|}}`$ $`=`$ $`\sqrt{3}\sqrt{2}A\left({\displaystyle \frac{4\sqrt{3}}{3}}{\displaystyle \frac{9}{2\mathrm{\Gamma }}}\right)\left(A^2+\rho ^2\right)\pm \sqrt{ϵ}`$ (46)
$`ϵ`$ $``$ $`{\displaystyle \frac{4}{3}}\rho ^4+{\displaystyle \frac{32}{3}}A^2\rho ^2+{\displaystyle \frac{8\sqrt{6}}{3}}A\rho ^2+\rho ^2`$ (48)
$`+{\displaystyle \frac{4}{3}}\rho ^3\left(4\sqrt{2}A+\sqrt{3}\right)\mathrm{cos}\left(3\theta \right),`$
where we introduce the notation

$`A`$ $``$ $`{\displaystyle \frac{\sqrt{\mathrm{\Gamma }}}{3}}q_{11},\rho \sqrt{B^2+C^2}`$ (49)
$`B`$ $``$ $`{\displaystyle \frac{\sqrt{\mathrm{\Gamma }}}{3}}q_{12}\rho \mathrm{sin}\theta ,C{\displaystyle \frac{\sqrt{\mathrm{\Gamma }}}{3}}q_{13}\rho \mathrm{cos}\theta `$ (50)
We see that $`\mathrm{cos}3\theta `$ should be $`+1`$ to minimize the ground state energy. Hence the degeneracy of ground states is not continuous anymore and has become 3-fold. This feature agrees with the numerical result. The ground state electronic wavefunction of $`\theta =0`$ is shown in Fig. 4. A rotation which brings $`\widehat{z}`$ to $`\widehat{x}`$ $`(\widehat{y})`$ will generate the wavefunctions of $`\theta =2\pi /3`$ $`(\theta =4\pi /3)`$.

## VII Numerical Results

Now we consider the full Hamiltonian $`=_t+_J+_{\mathrm{ep}}+_\mathrm{L}`$ for all clusters examined in Sec. IV. FM spin alignment facilitates hopping and causes energy lowering from delocalization, therefore encourages the polaron to grow. However, as $`\mathrm{\Gamma }`$ increases, the JT splitting will become the dominating influence on ground state energy. Greater localization enhances the JT energy lowering, which increases localization of the electron. On the other hand, $`_J`$ and $`_\mathrm{L}`$ serve as penalties for spin mis-alignment and lattice distortions. Our numerical studies find the optimal resolution of the competition between these effects. The 7-site cluster becomes favored from $`\mathrm{\Gamma }>0.18`$, as shown in Fig. 5. and Fig. 6. For all clusters considered, when $`\mathrm{\Gamma }`$ becomes large enough, the size of the ground state wavefunction shrinks to become that of the 7-site polaron, as shown in Fig. 7. Enlarging the size of the FM cluster to enhance delocalization energy is then disfavored by the strong lattice polaron effect. It is also clear that for extremely large $`\mathrm{\Gamma }`$, the 1-site lattice polaron will be the only form of electron state which exists.

Our numerical calculation predicts the lattice distortion pattern of the 7-site ground state. For $`\mathrm{\Gamma }=0.25`$, $`t=0.75`$ eV, and $`K=27.2`$ eV/$`\AA ^2`$ (obtained from Raman scattering in LaMnO3), the ground state shown in Fig. 4 has oxygen displacement parameters $`q_{11}1.1`$, $`q_{13}0.78`$ and $`q_{12}=0`$, which gives an outward displacement of $`0.38\AA `$ in the $`\widehat{z}`$ direction, and smaller outward displacements of $`0.036\AA `$ in both $`\widehat{x}`$ and $`\widehat{y}`$ directions, for the 6 oxygens surrounding the central Mn. Displacements of oxygens in the intermediate and outer layers are at least 10 times smaller. As predicted perturbatively, $`t_{1u}`$, $`t_{2u}`$, $`a_{2g}`$, $`q_{42}`$ and $`q_{43}`$ distortions are absent.

## VIII Discussion

When doping $`x`$ is non-zero, one should ask whether localized polaron solutions will distribute homogeneously or will attract, causing phase separation . We have not addressed this issue, which requires a more complicated calculation with additional Coulomb parameters in the Hamiltonian. Experiment is consistent with a concentration interval up to $`x=0.08`$ where polarons are homogeneously distributed. Our model shows that by this concentration, randomly-distributed 7-site polarons will overlap significantly. However, our model also shows that at concentrations $`x>0.045`$, polarons should be unstable relative to an undistorted ground state with FM spin order and metallic conduction by the doped electrons. This effect is not seen in experiments. Apparently alternate ground states, possibly involving organization of polaronic distortions, occur and enable the system to remain non-metallic.

Without additional physics (such as defects), our model cannot account for the observation  that La concentrations $`x`$ less than 0.02 yield less excess moment than expected from 7-site polarons.

Our model describes the competing spin and lattice polaron effects. We believe that it contains the main features needed to describe the system. A test would be measurement of the oxygen displacements which our model predicts. The model omits non-adiabatic phonon effects, spin quantization, temperature, and polaron-polaron interactions. For higher doping levels or $`T>0`$, these may have a larger influence and present challenges which could be worth pursuing if experimental guidance improves.

## Acknowledgment

We thank J. J. Neumeier for suggesting this investigation; J. J. Neumeier and J. L. Cohn for comments on the manuscript, and V. Perebeinos and A. Abanov for discussions. This work was supported by NSF grant No. DMR-0089492.