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# Point X-ray sources in the SNR G 315.4-2.30 (MSH 14-63, RCW 86)

## 1 Introduction

G 315.4$-$2.30 (MSH 14$-$63, RCW 86) is a bright (in both radio and X-ray) shell-like supernova remnant (SNR) with a peculiar protrusion to the southwest (e.g. Dickel et al. dic01 (2001), Vink et al. vin97 (1997)). This protrusion encompasses a bright hemispherical optical nebula (Rodger et al. rod60 (1960), Smith smi97 (1997); see also Fig. 3). The characteristic angular size of the SNR is about $`40^{^{}}`$, that at a distance to the remnant of 2.8 kpc (Rosado et al. ros96 (1996)) corresponds to $`32`$ pc. The radius of the optical nebula is $`2^{^{}}`$ (or $`1.6`$ pc). A collection of observational data points to the young age (few thousand years) of the SNR (see e.g. Dickel et al. dic01 (2001)).

Vink et al. (vin97 (1997)) put forward the idea that the SNR G 315.4$``$2.30 is the result of a supernova (SN) explosion inside a pre-existing wind-driven cavity (see also Dickel et al. dic01 (2001), Vink et al. vin02 (2002)) and noted that the elongated shape of the SNR resembles that of a wind-driven cavity created by a moving massive star (see Weaver et al. wea77 (1977) and Brighenti & D’Ercole bri94 (1994) for details). On the other hand, it is believed that the origin of the southwest protrusion is due to the interaction of the SN blast wave with a density enhancement in the ambient interstellar medium. However, as was correctly noted by Dickel et al. (dic01 (2001)), the density enhancement (e.g. a high-density cloud) should result in a concave dent in the shell, not in a protrusion. Dickel et al. (dic01 (2001)) also suggested that this protrusion “is perhaps the key to what is going on”.

We agree with the idea that G 315.4$``$2.30 is a diffuse remnant of an off-centered cavity SN explosion and supplement this idea by the suggestion that the massive SN progenitor star exploded near the edge of the main-sequence bubble. This suggestion implies that the southwest protrusion is the remains of a bow shock-like structure created in the interstellar medium by the post-main-sequence winds (see Sect. 4 and Gvaramadze gva02 (2002); cf. Wang et al. wan93 (1993)) and that the SN exploded near the center of this hemispherical structure. Given the youth of the SNR and assuming a reasonable kick velocity for the stellar remnant, one can expect that the stellar remnant should still be within the protrusion. Motivated by these arguments, Gvaramadze (gva02 (2002)) searched for a possible compact X-ray source to the southwest of G 315.4$``$2.30 using the ROSAT archival data, but the moderate spatial resolution of the ROSAT PSPC precluded detection of point sources against the bright background emission of the SNR’s shell.

In this paper we report the discovery of two point X-ray sources near the center of the hemispherical optical nebula using the archival Advanced CCD Imaging Spectrometer (ACIS) data of the Chandra X-Ray Observatory. We interpret one of the sources as a foreground active star of late spectral type, and the second one as a candidate stellar remnant (neutron star).

Note that Vink et al. (vin00 (2000)) also reported the discovery of a point X-ray source in the southwest half of G 315.4$``$2.30, at about $`7^{^{}}`$ from the geometrical center of the SNR. We recall that Vink et al. (vin97 (1997)) suggested that the SN blast wave in this SNR takes on the shape of the pre-existing elongated cavity (created by the stellar wind of the moving SN progenitor star). However, the initially spherical shape of the wind-driven cavity could be significantly affected by the stellar motion only if the massive star reaches the edge of the cavity and the stellar wind starts to interact directly with the ambient interstellar medium (e.g. Weaver et al. wea77 (1977)); this implies that the SN explodes near the edge of the future (young) SNR (see Sect. 4). However, the source discovered by Vink et al. (vin00 (2000)) is located too far from the edge of G 315.4$``$2.30. Moreover, the spectral characteristics of the source and the presence of a possible optical counterpart suggest that it is an active star rather than the stellar remnant associated with the SNR (Vink et al. vin00 (2000); see also Sect. 3.1).

## 2 Point X-ray sources

### 2.1 X-ray images

Fig. 1 shows the Chandra (0.7$``$2 keV) image of the highly structured southwest corner of the SNR G 315.4$``$2.30. Two point X-ray sources are clearly visible at the northwest of the image at $`\alpha _{2000}=14^\mathrm{h}40^\mathrm{m}31\stackrel{s}{.}33,\delta _{2000}=62^{}38^{^{}}22\stackrel{}{.}8`$ and $`\alpha _{2000}=14^\mathrm{h}40^\mathrm{m}31\stackrel{s}{.}05,\delta _{2000}=62^{}38^{^{}}16\stackrel{}{.}9`$. For both sources we measured a FWHM of $`1\stackrel{}{.}1`$, which is consistent with the Chandra point spread function at the off-axis angle $`2\stackrel{}{.}5`$. Fig. 2 shows a close-up of the region around the sources, labelled S (southern source) and N (northern source).

### 2.2 Optical images

Fig. 3 shows the image of the hemispherical optical nebula to the southwest of the SNR G 315.4$``$2.30 from the Digital Sky Survey (DSS-2, red plates). Fig. 4 shows an enlarged view of the region around the point X-ray sources. The source S is in good positional agreement with a point-like object immersed in a diffuse optical filament. This object is indicated in the HST Guide Star Catalog as non-stellar, with a photographic magnitude of $`13.38\pm 0.40`$. We believe, however, that it was misclassified due to the effect of the background diffuse emission and in fact it is a star.

The source N has no optical counterpart to a limiting magnitude $`21`$.

### 2.3 Spectral analysis

The spectra of the point sources were extracted from circular regions with radii of $`1.5`$ arcsec. The background spectrum was taken from a circle with a radius of $`4.5`$ arcsec at 6.5 arcsec northeast of the point sources. The PSF model shows that the fraction of the source flux in the background region is negligible. The spectral modeling was performed in the 0.5$``$10 keV energy range using the XSPEC spectra fitting package. The estimates of the interstellar absorption, $`N_\mathrm{H}`$, towards G 315.4$``$2.30 are quite uncertain (cf. e.g. Vink et al. vin97 (1997) with Vink et al. vin02 (2002)), so the spectra were fitted with $`N_\mathrm{H}`$ as a free parameter. In one case, however, we used the fixed value of $`N_\mathrm{H}`$ (see below).

The spectrum of the source S is shown in Fig. 5;

the solid line represents the best fit optically thin plasma model, with a temperature $`=0.69\pm 0.05`$ keV, abundance $`=0.07\pm 0.02`$, $`N_\mathrm{H}=(1.2\pm 0.3)\times 10^{21}\mathrm{cm}^2`$, luminosity (in the 0.5-10 keV energy range) $`2.8\times 10^{31}\mathrm{erg}\mathrm{s}^1`$, and $`\chi ^2`$/d.o.f. =21.6/25. The blackbody or power law models give unacceptable fits.

The spectrum of the source N (shown in Fig. 6) can be fitted almost equally well with a power law (PL), two-temperature blackbody (BB$`+`$BB), or blackbody plus power law (BB$`+`$PL) models. A simple BB model gives unacceptable fits. The best fit spectrum predicted by the BB$`+`$PL model is shown in Fig. 6 by the solid line.

We note that the best fit PL model requires $`N_\mathrm{H}=0`$ (we consider this fact as an indication of the galactic origin of the source N), although models with $`N_\mathrm{H}`$ up to $`1.5\times 10^{21}\mathrm{cm}^2`$ (presented in Table 1) also give acceptable fits.

The results of a spectral analysis for the source N are summarized in Table 1.

## 3 Discussion

### 3.1 Source S

The soft X-ray spectrum of the source S and the existence of the candidate optical counterpart strongly suggest that this source is an active star. Assuming that S is indeed a star and given the observed X-ray to optical flux ratio, one can exclude the possibility that this star is of the OB-type. Therefore it cannot be a member of a group of OB stars located in the direction of G 315.4$``$2.30 nearly at the same distance as the SNR (Westerlund wes69 (1966)). Most likely the source S is a foreground active star of late spectral type. A follow-up study of this object could clarify its nature.

Note that the point X-ray source discovered by Vink et al. (vin00 (2000)) has much in common with the source S. The spectra of both sources are soft and could be fitted with the optically thin plasma model with depleted abundances (typical of late-type stars; e.g. Giampapa et al. gia96 (1996)). Both sources have candidate optical counterparts with almost the same photographic magnitudes. In both cases the X-ray to optical flux ratios suggest that the optical objects are late-type stars. Evidence for long-term variability of the former source (Vink et al. vin00 (2000)) also suggest that it is an active star.

### 3.2 Source N

The spectral characteristics of the source N coupled with the absence of an optical counterpart allow us to consider it as a candidate stellar remnant. We now discuss this possibility.

#### 3.2.1 Power law model

The PL fit of the spectrum (with the photon index typical of pulsars) suggest that the source N can be an active (rotation-powered) neutron star. Assuming that N is a pulsar111The $`3.2\mathrm{s}`$ individual exposure time of the ACIS instrument makes the search for short pulsations impossible. and using the empirical relationships between the non-thermal X-ray and spin-down luminosities of pulsars (e.g. Becker & Trümper bec97 (1995), Possenti et al. pos02 (2002)), one can estimate the latter, $`\dot{E}10^{35}d_{2.8}^2\mathrm{erg}\mathrm{s}^1`$, where $`d_{2.8}`$ is the distance to the SNR in units of 2.8 kpc.

The inferred low spin-down luminosity can be considered as an argument against the possibility that the source N is a young fast-rotating pulsar with a standard magnetic field ($`10^{11}10^{13}`$ G). Therefore N can be either a young pulsar born with a low surface magnetic field (e.g. Blandford et al. bla83 (1983), Urpin et al. urp86 (1986)) and/or a large rotation period (e.g. Spruit & Phinney spr98 (1998)) or an aged pulsar with a decaying magnetic field. The first possibility would deserve detailed consideration if a candidate period of 12 ms found for the central X-ray source in Cas A (Murray et al. 2002a ) is confirmed by an independent timing analysis. The second one implies that N is an old pulsar (of an arbitrary age) projected by chance on the SNR G 315.4$``$2.30.

Note, however, that the above-mentioned empirical relationships are quite uncertain and should be used with caution. For example, the 267 ms radio pulsar PSR B 1853+01 associated with the SNR W 44 (Wolszczan et al. wol91 (1991)) has almost the same spin-down luminosity ($`4\times 10^{35}\mathrm{erg}\mathrm{s}^1)`$ as that derived above for the source N, while the characteristic age of the pulsar ($`2\times 10^4`$ yr; consistent with a range of ages derived for W 44 using the standard Sedov-Taylor model \[see Smith et al. smi85 (1985)\]) points to its relative youth. On the other hand, the pulsar PSR B 1853+01 could be much older if its high spin-down rate ($`\dot{P}0.2\times 10^{12}\mathrm{s}\mathrm{s}^1`$) is connected to the interaction between the pulsar’s magnetosphere and the dense circumstellar matter222The large dispersion measure variations inherent to this pulsar (Jacoby & Wolszczan jac99 (1999)) could be considered as an indirect support of this suggestion. (cf. Gvaramadze gva01 (2001)). The age of W 44 also could be much greater if the origin of this mixed-morphology SNR is due to the cavity SN explosion (cf. Gvaramadze gva02 (2002)).

The uncertainties inherent to the empirical relationships are more obvious in the case of the pulsar PSR J 0205$+$6449, recently discovered in the SNR 3C 58. The spin-down luminosity of this young (characteristic age $`5400`$ yr) pulsar is $`2.6\times 10^{37}\mathrm{erg}\mathrm{s}^1`$ (Murray et al. 2002b ), while its (non-thermal; see Slane et al. sla02 (2002)) X-ray luminosity is $`2.1\times 10^{32}d_{2.6}^2\mathrm{erg}\mathrm{s}^1`$, i.e. about two orders of magnitude less than that predicted by the empirical relationships. The disparity between the predicted and observed non-thermal luminosities is even higher in the case of another young pulsar – the Vela pulsar (Pavlov et al. pav01 (2001)). Note that the photon indices and non-thermal luminosities of these two pulsars are almost the same as those predicted for the source N by the PL (or BB$`+`$PL) model, while their characteristic ages are of the same order of magnitude as the age of the SNR G 315.4$``$2.30 inferred in Sect. 4. Therefore one cannot exclude that the source N is a young pulsar with “ordinary” parameters. This should be tested observationally.

#### 3.2.2 Two-temperature blackbody model

In the two-temperature blackbody model, the origin of the soft component can be attributed to the cooling surface of a neutron star, while the hard component to the polar caps heated by the backflow of relativistic particles (e.g. Wang et al. wan98 (1998)).

The best-fit BB$`+`$BB model yields the temperature of the soft component of $`0.11`$ keV and the effective radius of 2.3 km. The inferred temperature is somewhat larger than that predicted by standard cooling models (e.g. Page pag98 (1998)), while the radius is significantly smaller than the radius of the neutron star. In principle, one can expect that the use of realistic neutron star atmosphere models (e.g. Pavlov et al. pav95 (1995)) would adjust these parameters to acceptable values. But the interpretation of the hard component is more problematic. The effective polar cap area inferred from the best-fit BB$`+`$BB model ($`10^8\mathrm{cm}^2`$) is too small and the observed temperature is too large to be consistent with models for heating of polar caps (e.g. Wang et al. wan98 (1998) and references therein). Therefore we consider this model as unplausible and suggest that at least at high energies the X-ray emission of the source N is non-thermal.

#### 3.2.3 Blackbody plus power law model

The use of the BB$`+`$PL model assumes that the soft X-ray emission comes from the entire surface of a cooling neutron star or from some smaller hot areas, while the hard X-rays are due to the non-thermal magnetospheric emission.

The best fit BB$`+`$PL model shows that the spectrum of the source N is dominated by the non-thermal emission at energies $`>1`$ keV, and suggests the existence of a soft thermal component. However, the unknown interstellar absorption and uncertainties due to the time-dependent decrease in ACIS low-energy quantum efficiency make the estimates of the flux and bolometric luminosity of the BB component unconstrained. The best fit model with $`N_\mathrm{H}`$ as a free parameter (see Table 1) requires large interstellar absorption and consequent large bolometric luminosity. Although the large absorption, in principle, is consistent with values derived by Vink et al. (vin02 (2002)) for the SNR G 315.4$``$2.30, the large inferred bolometric luminosity implies an uncomfortably large effective radius of $`60`$ km. The normalization of the BB component, however, is plausible for lower values of $`N_\mathrm{H}`$. A more detailed consideration of this problem will be possible only with updated Chandra calibration at low energies. Note that dense clumps of circumstellar matter (the natural products of interaction between post-main-sequence winds of the SN progenitor star; e.g. Gvaramadze gva01 (2001) and references therein; see also Sect. 4) could add a significant contribution to the neutral hydrogen absorption towards the source N, as well as possibly causing the enhanced absorption towards the central compact source in Cas A (required by some model fits of its spectrum; e.g. Murray et al. 2002a ).

Note also that at present we cannot definitively confirm or reject the existence of a soft BB component. Therefore we consider the PL model with a reasonable value of $`N_\mathrm{H}`$ as a good approximation for the spectrum of the source N. The follow-up multiwavelength observations of this source, including the search for pulsed emission, long term variability, and radio, optical or $`\gamma `$-ray counterparts, may provide crucial information for an understanding of its nature and therefore are highly desirable.

## 4 SNR G 315.4$``$2.30

We now briefly discuss a scenario for the origin of the SNR G 315.4$``$2.30 (the more detailed description will be presented elsewhere). We note that our scenario has much in common with the model proposed by Wang et al. (wan93 (1993)) to explain the origin of large-scale structures around the SN 1987A, and suggest that G 315.4$``$2.30 is an older version of the latter.

We believe that the SNR G 315.4$``$2.30 is the result of a cavity SN explosion of a moving massive star, which after the main-sequence (MS) phase (lasting $`10^7`$ yr) has evolved through the red supergiant (RSG) phase ($`10^6`$ yr), and then experienced a short ($`10^4`$ yr) “blue loop” (i.e. the zero-age MS mass of the star was $`1520M_{}`$). During the MS phase the stellar wind (with the mechanical luminosity, $`L`$, of $`10^{35}\mathrm{erg}\mathrm{s}^1`$) blows a large-scale bubble in the interstellar medium. The bubble eventually stalls at radius $`R_{\mathrm{st}}12(L_{35}/n)^{1/2}\mathrm{pc}`$ in time $`t_{\mathrm{st}}10^6(L_{35}/n)^{1/2}\mathrm{yr}`$, where $`L_{35}=L/10^{35}\mathrm{erg}\mathrm{s}^1`$ and $`n`$ is the number density of the interstellar gas. The current radius of SNR G 315.4$``$2.30 is $`16`$ pc. The motion of that star causes it to cross the stalled bubble and start to interact directly with the unperturbed interstellar gas. This happens at time $`t_{\mathrm{cr}}R_{\mathrm{st}}/v_{}=2.4\times 10^6(L_{35}/n)^{1/2}v_{,5}^1\mathrm{yr}`$, where $`v_{,5}`$ is the stellar velocity in units of $`5\mathrm{km}\mathrm{s}^1`$. The time is in agreement with the duration of the MS phase if $`v_{}1\mathrm{km}\mathrm{s}^1`$. In this case the SN progenitor star enters in the RSG phase while it is near the edge of the MS bubble. During the relatively short RSG phase, the star loses most (two thirds) of its initial mass in the form of a dense, slow wind. The interaction of the RSG wind with the interstellar medium results in the origin of a bow shock-like structure with a characteristic radius, $`r`$, determined by the relationship: $`\dot{M}_{\mathrm{RSG}}v_{\mathrm{RSG}}/4\pi r^2n(2kT+m_\mathrm{H}v_{}^2)`$, where $`\dot{M}_{\mathrm{RSG}}`$ and $`v_{\mathrm{RSG}}`$ are, correspondingly, the mass-loss rate and wind velocity during the RSG phase, $`T`$ is the temperature of the ambient interstellar medium, $`k`$ is the Boltzmann constant, and $`m_\mathrm{H}`$ is the mass of a hydrogen atom. For $`n1\mathrm{cm}^3`$ (Smith smi97 (1997), Ghavamian et al. gha01 (2001)), $`\dot{M}_{\mathrm{RSG}}=10^5M_{}\mathrm{yr}^1`$, $`v_{\mathrm{RSG}}=10\mathrm{km}\mathrm{s}^1`$, $`T=8000`$ K, and $`v_{}=1\mathrm{km}\mathrm{s}^1`$, one has $`r1.5`$ pc. This value is in a comfortable agreement with the radius of the hemispherical optical nebula in the southwest of G 315.4$``$2.30 ($`1.6`$ pc).

About $`10^4`$ yr before the SN explosion the progenitor star becomes a blue supergiant whose fast wind sweeps the material of the RSG wind. We speculate that at the moment of SN explosion the blue supergiant wind was trapped in the southwest direction by the dense material of the bow shock-like structure, while in the opposite direction it was able to break out in the low-density MS bubble, so that the SN explodes inside a “hollow” hemispherical structure open towards the MS bubble.

The SN blast wave expands almost freely across the low-density MS bubble (for the explosion energy of $`10^{51}`$ erg and mass of the SN ejecta of $`3.5M_{}`$, the expansion velocity of the blast wave is $`v_{\mathrm{bl}}\mathrm{5\hspace{0.17em}000}\mathrm{km}\mathrm{s}^1`$) and reaches the northeast edge of the bubble after $`4.7\times 10^3`$ yr. The density jump at the edge of the bubble results in the abrupt deceleration of the blast wave to a velocity of $`(\beta n_\mathrm{b}/n)^{1/2}v_{\mathrm{bl}}600800\mathrm{km}\mathrm{s}^1`$ (the values derived from studies of Balmer-dominated filaments encircling the SNR G 315.4$``$2.30; Long & Blair lon90 (1990) and Smith smi97 (1997)), where $`\beta 5`$ (e.g. Sgro sgr75 (1975)). This deceleration implies a density jump of a factor of $`200300`$ or a number density of the MS bubble gas $`n_\mathrm{b}0.0030.005\mathrm{cm}^3`$, i.e. a reasonable value given the mass lost during the MS phase is $`0.5M_{}`$.

In the southwest direction, however, the expansion of the SN blast wave is hampered by the dense hemispherical circumstellar shell. The shocked remains of this shell are now seen as the bright southwest protrusion (shown in Fig. 3). The existence of radiative filaments in this corner of the SNR implies that the blast wave slows down to the velocity of $`100\mathrm{km}\mathrm{s}^1`$, that in its turn implies the density contrast of $`\mathrm{15\hspace{0.17em}000}`$. For $`n_\mathrm{b}=0.003\mathrm{cm}^3`$, one has the number density of the circumstellar material of $`50\mathrm{cm}^3`$, i.e. in a good agreement with the density estimate derived by Leibowitz & Danziger (lei83 (1983)). On the other hand, the recent discovery of Balmer-dominated filaments protruding beyond the radiative arc (see Fig. 3 of Smith smi97 (1997) and Fig. 4 of Dickel et al. dic01 (2001)) suggests that the SN blast wave has partially overrun the clumpy circumstellar shell (cf. Franco et al. fra91 (1991)) and now propagates through the interstellar medium. We believe that this effect is responsible for the complicated appearance of the southwest corner of the SNR. For the radial extent of protrusions of $`2`$ pc, and assuming that their mean expansion velocity is $`700\mathrm{km}\mathrm{s}^1`$, one has that the blowouts occured $`3\times 10^3`$ yr ago.

## 5 Conclusion

We have analyzed the archival Chandra X-Ray Observatory data on G 315.4$``$2.30 to search for a stellar remnant in the southwest corner of this SNR. The search was motivated by the hypothesis that the SNR G 315.4$``$2.30 is the result of an off-centered cavity SN explosion of a moving massive star, which ends its evolution just near the edge of the main-sequence wind-driven bubble. This hypothesis implies that the southwest protrusion in G 315.4$``$2.30 is the shocked material of a pre-existing circumstellar structure and that the actual location of the SN blast center is near the center of this structure. We have discovered two point X-ray sources in the “proper” place. One of the sources is interpreted as a foreground active star of late spectral type, while the second one as a candidate neutron star (perhaps a young “ordinary” pulsar). The follow-up observations of these sources will help us to understand their nature and thereby to test the hypothesis of the origin of the SNR G 315.4$``$2.30.

###### Acknowledgements.

We are grateful to J.R.Dickel (the referee) for useful suggestions and comments.


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# Kinetics of photoinduced anisotropy in azopolymers: models and mechanisms

## I Introduction

The ability of some photosensitive materials to become dichroic and birefringent under the action of light is known as the effect of photoinduced optical anisotropy (POA). This effect provides a means of having the light-controlled anisotropy and it makes the materials that exhibit POA very promising for use in many photonic applications Prasad et al. (1995); Eich et al. (1987). Owing to extremely high efficiency of POA in side-chain polymers that contain covalently linked photochromic moieties such as azobenzene derivatives and are known as azopolymers, light induced ordering processes in these polymers have been the subject of intense experimental and theoretical studies in the last decade Eich et al. (1987); Hvilsted et al. (1992); Wiesner et al. (1992); Dumont et al. (1993); Fisher et al. (1994); Pederson and Michael (1997); Pederson et al. (1998); Natansohn et al. (1998); Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999).

A typical experimental procedure to induce optical anisotropy in azopolymers consists in irradiating a sample with polarized UV light. In this case the accepted though not very well understood mechanism of POA assumes that the key processes involved are induced trans–cis-photoisomerization and subsequent thermal and/or photochemical cis–trans-back-isomerization of the azobenzene moieties.

These trans–cis–trans photoisomerization cycles are accompanied by rotations of the azobenzene chromophores. Since the transition dipole moment of the azobenzene moiety is directed along its long molecular axis, the fragments oriented perpendicular to the incident actinic light polarization vector, $`𝐄`$, are almost inactive. The long axes of the azobenzene fragments tend to become oriented along directions normal to the polarization vector $`𝐄`$. Non-photoactive groups then undergo reorientation due to cooperative motion or dipole interaction Natansohn et al. (1998); Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999).

The above scenario assumes angular redistribution of the long axes of the *trans* molecules during the trans–cis–trans isomerization cycles. It is known as the photoorientation mechanism that was initially suggested in Ref. Neporent and Stolbova (1963) for the case, where the lifetime of *cis* state is short. This state becomes temporary populated during photoisomerization but reacts immediately back to thermodynamically stable *trans* isomeric form.

Another limiting case – the so-called angular selective hole burning mechanism (photoselection) – occurs when the *cis* states are long-living. In this case POA is caused by the selective depletion of the *trans* isomeric form when reaching the steady state Dumont et al. (1993). The anisotropy induced in this way is not long term stable and disappears as a result of the thermal back reaction.

In both cases the effect is primary governed by the dependence of photoisomerization rates on orientation of the photoactive groups. From the other hand, we have also seen that physical characteristics of POA can be different depending on a number of additional factors such as lifetime of the *cis* form. These factors will determine kinetics of POA that describes how amount of photoinduced anisotropy characterized by absorption dichroism or birefringence evolves in time upon illumination and after switching it off.

In particular, as opposed to the reversible POA, where anisotropy disappears after switching off the irradiation Neporent and Stolbova (1963); Todorov et al. (1983); Dumont and Sekkart (1992, 1993); Dumont (1996), POA can be long term stable. This is the case for POA in liquid crystalline (LC) azopolymers. Theoretically, it means that the photo-reorientation in LC azopolymers is a non-equilibrium process in a rather complex polymer system and it still remains a challenge to develop a tractable microscopic theory treating the effect adequately.

In this paper we present theoretical considerations concerning the kinetics of POA by starting from kinetic rate equations of general form and assuming that reorientation of the azobenzene groups results in the appearance of a self-consistent anisotropic field that support the photoinduced anisotropy. This field is thought of as being caused by anisotropic interactions between the azobenzene fragments and rearrangement of the main chains and other non-absorbing fragments.

There are two phenomenological models based on similar assumptions: the mean field model proposed in Ref. Pederson and Michael (1997); Pederson et al. (1998) and the model with additional order parameter attributed to the polymer backbone Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999). Both these models, though they look different, incorporate the long term stability by introducing additional degree of freedom (subsystem) which kinetics reflects cooperative motion and account for non-equilibrium behavior.

In Sec. II we discuss physical assumptions underlying general structure of the phenomenological models and show that it is determined by the angular redistribution probabilities and the order parameter correlation functions. We use the results of general analysis to formulate a simple model of the photoinduced ordering in LC azopolymers. In addition to the long term stability of POA, this model accounts for biaxiality of the photoinduced orientational structures Wiesner et al. (1992); Kiselev et al. (2001); Yaroshchuk et al. (2001a, b, c); Sajti et al. (2001) that was neglected in the models of Refs. Pederson and Michael (1997); Pederson et al. (1998); Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999).

In Sec. III we compute order parameter components and fractions of the azobenzene units for different irradiation doses. Then we use the results of numerical analysis to fit the experimental data on photoinduced dichroism of absorption. These data demonstrate that for long-living *cis* forms dependencies of the absorption dichroism on the illumination time can be qualitatively different depending the wavelength of exciting beam. We find that the different regimes can be explained by using our model and the calculated dependencies are in good agreement with the data obtained experimentally.

Finally, in Sec. IV we draw together the results and make some concluding remarks.

## II Model

We shall assume that the dye molecules in the ground state are of *trans* form and the orientation of the molecular axis is defined by the unit vector $`\widehat{𝐧}=`$($`\mathrm{sin}\theta \mathrm{cos}\varphi `$,$`\mathrm{sin}\theta \mathrm{sin}\varphi `$, $`\mathrm{cos}\theta `$), where $`\theta `$ and $`\varphi `$ are Euler angles of the unit vector. Angular distribution of the *trans* molecules at time $`t`$ is characterized by the number distribution function $`N_{tr}(\widehat{𝐧},t)`$. Similarly, molecules in the excited state have the *cis* conformation and are characterized by the function $`N_{cis}(\widehat{𝐧},t)`$. Then the number of *trans* and *cis* molecules is given by

$$N_{tr}(t)Nn_{tr}(t)=N_{tr}(\widehat{𝐧},t)d\widehat{𝐧},$$
(1)
$$N_{cis}(t)Nn_{cis}(t)=N_{cis}(\widehat{𝐧},t)d\widehat{𝐧},$$
(2)
$$n_{tr}(t)+n_{cis}(t)=1,$$
(3)
where $`{\displaystyle d\widehat{𝐧}}{\displaystyle _0^{2\pi }}d\varphi {\displaystyle _0^\pi }\mathrm{sin}\theta \mathrm{d}\theta `$ and $`N`$ is the total number of molecules. The normalized angular distribution functions, $`f_\alpha (\widehat{𝐧},t)`$, of *trans* ($`\alpha =tr`$) and *cis* ($`\alpha =cis`$) molecules can be conveniently defined by the relation

$$N_\alpha (\widehat{𝐧},t)=Nn_\alpha (t)f_\alpha (\widehat{𝐧},t).$$
(4)
We also need to introduce additional angular distribution function $`f_p(\widehat{𝐧},t)`$ characterizing the anisotropic field due to interaction between a side chain fragment and nearby molecules. In particular, this field is affected by collective degrees of freedom of non-absorbing units such as main chains and determines angular distribution of the molecules in the stationary regime. It bears close resemblance to the equilibrium distribution of the mean field theories of POA. In Refs. Pederson and Michael (1997); Pederson et al. (1998); Sajti et al. (2001) this distribution has been assumed to be proportional to $`\mathrm{exp}(V(\widehat{𝐧})/k_BT)`$, where $`V(\widehat{𝐧})`$ is the mean-field potential that depends on the order parameter tensor.

In other words, we have the additional subsystem characterized by $`f_p(\widehat{𝐧},t)`$ attributed to the presence of long-living angular correlations coming from anisotropic interactions between side chain groups and collective modes of polymeric environment. For brevity, we shall refer to the subsystem as a polymer system (matrix). We shall write the kinetic rate equations for $`N_\alpha (\widehat{𝐧},t)`$ in the form of master equations Gardiner (1985); van Kampen (1984):

$`{\displaystyle \frac{N_\alpha }{t}}=\left[{\displaystyle \frac{\mathrm{d}N_\alpha }{\mathrm{d}t}}\right]_{\mathrm{Diff}}+{\displaystyle \underset{\beta \alpha }{}}{\displaystyle }[W(\alpha ,\widehat{𝐧}|\beta ,\widehat{𝐧}^{})`$
$`\times N_\beta (\widehat{𝐧}^{},t)W(\beta ,\widehat{𝐧}^{}|\alpha ,\widehat{𝐧})N_\alpha (\widehat{𝐧},t)]\mathrm{d}\widehat{𝐧}^{}`$
$`+\gamma _\alpha [N_\alpha (t){\displaystyle }\mathrm{\Gamma }_{\alpha p}(\widehat{𝐧},\widehat{𝐧}^{})f_p(\widehat{𝐧}^{},t)\mathrm{d}\widehat{𝐧}^{}`$
$`N_\alpha (\widehat{𝐧},t)],`$ (5)
where $`\alpha ,\beta \{tr,cis\}`$.

The first term on the right hand side of Eq. (5) is due to rotational diffusion of molecules in *trans* ($`\alpha =tr`$) and *cis* ($`\alpha =cis`$) conformations. In frictionless models this term is absent and will be dropped in our subsequent notations.

Now we need to specify the rate of $`transcis`$ photoisomerization stimulated by the incident UV light. For the electromagnetic wave linearly polarized along the $`x`$–axis the transition rate can be written as follows Dumont and Sekkart (1992); Dumont (1996):

$`W(cis,\widehat{𝐧}|tr,\widehat{𝐧}^{})=\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})P_{tr}(\widehat{𝐧}^{}),`$ (6)
$`P_{tr}(\widehat{𝐧})=(\mathrm{}\omega _t)^1\mathrm{\Phi }_{trcis}{\displaystyle \underset{i,j}{}}\sigma _{ij}^{(tr)}(\widehat{𝐧})E_iE_j^{}`$
$`=q_tI(1+un_x^2),`$ (7)
where $`𝝈^{(tr)}(\widehat{𝐧})`$ is the tensor of absorption cross section for the *trans* molecule oriented along $`\widehat{𝐧}`$: $`\sigma _{ij}^{(tr)}=\sigma _{}^{(tr)}\delta _{ij}+(\sigma _{||}^{(tr)}\sigma _{}^{(tr)})n_in_j`$; $`u(\sigma _{||}^{(tr)}\sigma _{}^{(tr)})/\sigma _{}^{(tr)}`$ is the absorption anisotropy parameter; $`\mathrm{}\omega _t`$ is the photon energy; $`\mathrm{\Phi }_{trcis}`$ is the quantum yield of the process and $`\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})`$ describes the angular redistribution of the molecules excited in the *cis* state; $`I`$ is the pumping intensity and $`q_t(\mathrm{}\omega _t)^1\mathrm{\Phi }_{trcis}\sigma _{}^{(tr)}`$.

Similar line of reasoning applies to the $`cistrans`$ transition, so we have

$`W(tr,\widehat{𝐧}|cis,\widehat{𝐧}^{})=\gamma _c\mathrm{\Gamma }_{ct}^{(sp)}(\widehat{𝐧},\widehat{𝐧}^{})`$
$`+q_cI\mathrm{\Gamma }_{ct}^{(ind)}(\widehat{𝐧},\widehat{𝐧}^{}),`$ (8)
where $`q_c(\mathrm{}\omega _t)^1\mathrm{\Phi }_{cistrans}\sigma ^{(cis)}`$ and $`\gamma _c1/\tau _c`$, $`\tau _c`$ is the lifetime of *cis* molecule and the anisotropic part of the absorption cross section is disregarded, $`\sigma _{||}^{(cis)}=\sigma _{}^{(cis)}\sigma ^{(cis)}`$. Eq. (II) implies that the process of angular redistribution for induced and spontaneous transitions can differ. Note that the normalization condition for all the angular redistribution probability intensities is

$$\mathrm{\Gamma }_{\beta \alpha }(\widehat{𝐧},\widehat{𝐧}^{})d\widehat{𝐧}=1.$$
(9)
From Eqs. (5), (6) and (II) it is not difficult to obtain equation for $`n_{tr}(t)`$:

$$\frac{n_{tr}}{t}=(\gamma _c+q_cI)n_{cis}P_{tr}_{tr}n_{tr},$$
(10)
where the angular brackets $`\mathrm{}_\alpha `$ stand for averaging over angles with the distribution function $`f_\alpha `$ . Owing to the condition (9), this equation does not depend on the form of the angular redistribution probabilities.

The last square bracketed term on the right hand side of Eq. (5) describes the process that equilibrates the side chain absorbing molecules and the polymer system in the absence of irradiation. The angular redistribution probabilities $`\mathrm{\Gamma }_{\alpha p}(\widehat{𝐧},\widehat{𝐧}^{})`$ meet the normalization condition, so that thermal relaxation does not change the total fractions $`N_{tr}`$ and $`N_{cis}`$. If there is no angular redistribution, then $`\mathrm{\Gamma }_{\alpha p}(\widehat{𝐧},\widehat{𝐧}^{})=\delta (\widehat{𝐧}\widehat{𝐧}^{})`$ and both equilibrium angular distributions $`f_{tr}^{(eq)}`$ and $`f_{cis}^{(eq)}`$ are equal to $`f_p`$.

We can now derive the mean field models considered in Refs. Pederson and Michael (1997); Pederson et al. (1998); Sajti et al. (2001) by putting $`\gamma _c=0`$ (long-living *cis* fragments), $`\gamma _{cis}=\gamma _{tr}`$ and assuming that the angular redistribution probabilities $`\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})`$ and $`\mathrm{\Gamma }_{ct}(\widehat{𝐧},\widehat{𝐧}^{})`$ are equal to the equilibrium distribution, $`f_p=p(\widehat{𝐧})`$, determined by the mean-field potential $`V(\widehat{𝐧})`$: $`p(\widehat{𝐧})\mathrm{exp}(V/k_BT)`$. In other words, this procedure implies that the angular redistribution operators act as projectors onto the angular distribution of polymer system. This is the order parameter dependent distribution that characterizes the orientation of azo dye molecules after isomerization.

An alternative and a more general approach is to determine the distribution function $`f_p(\widehat{𝐧},t)`$ from the kinetic equation that can be written in the following form:

$`{\displaystyle \frac{f_p(\widehat{𝐧},t)}{t}}={\displaystyle \underset{\alpha =\{tr,cis\}}{}}\gamma _p^{(\alpha )}n_\alpha (t)[f_p(\widehat{𝐧},t)`$
$`{\displaystyle }\mathrm{\Gamma }_{p\alpha }(\widehat{𝐧},\widehat{𝐧}^{})f_\alpha (\widehat{𝐧}^{},t)\mathrm{d}\widehat{𝐧}^{}].`$ (11)
Equations for the angular distribution functions $`f_{tr}(\widehat{𝐧},t)`$ and $`f_{cis}(\widehat{𝐧},t)`$ can be derived from Eq. (5) by using the relations (6)–(10). The result is as follows

$`n_{cis}{\displaystyle \frac{f_{cis}}{t}}=n_{tr}[P_{tr}_{tr}f_{cis}`$
$`{\displaystyle }\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})P_{tr}(\widehat{𝐧}^{})f_{tr}(\widehat{𝐧}^{},t)\mathrm{d}\widehat{𝐧}^{}]`$
$`\gamma _{cis}n_{cis}[f_{cis}`$
$`{\displaystyle }\mathrm{\Gamma }_{cisp}(\widehat{𝐧},\widehat{𝐧}^{})f_p(\widehat{𝐧}^{},t)\mathrm{d}\widehat{𝐧}^{}]`$ (12)
$`n_{tr}{\displaystyle \frac{f_{tr}}{t}}=n_{tr}\left[P_{tr}(\widehat{𝐧})P_{tr}_{tr}\right]f_{tr}`$
$`+\gamma _cn_{cis}{\displaystyle \mathrm{\Gamma }_{ct}^{(sp)}(\widehat{𝐧},\widehat{𝐧}^{})f_{cis}(\widehat{𝐧}^{},t)d\widehat{𝐧}^{}}`$
$`+q_cIn_{cis}{\displaystyle \mathrm{\Gamma }_{ct}^{(ind)}(\widehat{𝐧},\widehat{𝐧}^{})f_{cis}(\widehat{𝐧}^{},t)d\widehat{𝐧}^{}}`$
$`(\gamma _c+q_cI)n_{cis}f_{tr}\gamma _{tr}n_{tr}[f_{tr}`$
$`{\displaystyle }\mathrm{\Gamma }_{trp}(\widehat{𝐧},\widehat{𝐧}^{})f_p(\widehat{𝐧}^{},t)\mathrm{d}\widehat{𝐧}^{}].`$ (13)
Eq. (10) and Eqs. (11)–(13) can be regarded as a starting point for the formulation of a number of phenomenological models of POA. We have already shown that these models include the mean field theories considered in Refs. Pederson and Michael (1997); Pederson et al. (1998); Sajti et al. (2001).

An alternative model was suggested in Refs. Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999), where angular distribution of *cis* isomers is assumed to be stationary and isotropic, $`f_{cis}=(4\pi )^1`$. This assumption implies that

$$\gamma _{cis}=\gamma _p^{(cis)}=0$$
(14)
and $`\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})=f_{cis}`$. In order to ensure that $`f_p=f_{tr}`$ at the equilibrium state, this model uses the relation

$$\mathrm{\Gamma }_{\alpha p}(\widehat{𝐧},\widehat{𝐧}^{})=\mathrm{\Gamma }_{p\alpha }(\widehat{𝐧},\widehat{𝐧}^{})=\delta (\widehat{𝐧}\widehat{𝐧}^{}).$$
(15)
So, after neglecting biaxiality we can obtain the results of Refs. Puchkovs’ka et al. (1998); Yaroshchuk et al. (1999) by additionally putting $`\mathrm{\Gamma }_{ct}^{(sp)}(\widehat{𝐧},\widehat{𝐧}^{})=f_{tr}(\widehat{𝐧},t)`$ and $`\mathrm{\Gamma }_{ct}^{(ind)}(\widehat{𝐧},\widehat{𝐧}^{})=(4\pi )^1`$.

In this paper we consider another simple model by assuming that all the angular redistribution operators $`\mathrm{\Gamma }_{tc}`$ and $`\mathrm{\Gamma }_{ct}`$ take the following isotropic form:

$`\mathrm{\Gamma }_{ct}^{(sp)}(\widehat{𝐧},\widehat{𝐧}^{})=\mathrm{\Gamma }_{ct}^{(ind)}(\widehat{𝐧},\widehat{𝐧}^{})`$
$`=\mathrm{\Gamma }_{tc}(\widehat{𝐧},\widehat{𝐧}^{})={\displaystyle \frac{1}{4\pi }}f_{iso}.`$ (16)
Since we have neglected anisotropy of *cis* fragments in Eq. (II), it is reasonable to suppose that the equilibrium distribution of *cis* molecules is also isotropic, $`f_{cis}^{(eq)}=f_{iso}`$. From the other hand, the equilibrium angular distribution of *trans* fragments is determined by the polymer system: $`f_{tr}^{(eq)}=f_p`$. So, we can use Eqs. (14)–(16) to derive the system of kinetic equations from Eqs. (10)–(13). The result is given by

$`n_{cis}{\displaystyle \frac{f_{cis}}{t}}=n_{tr}P_{tr}_{tr}(f_{iso}f_{cis}),`$ (17a)
$`n_{tr}{\displaystyle \frac{f_{tr}}{t}}=\left(P_{tr}_{tr}P_{tr}\right)n_{tr}f_{tr}+(\gamma _c+q_cI)`$
$`\times n_{cis}(f_{iso}f_{tr})+\gamma _{tr}n_{tr}(f_pf_{tr}),`$ (17b)
$`{\displaystyle \frac{f_p}{t}}=\gamma _pn_{tr}(f_{tr}f_p),`$ (17c)
where $`\gamma _p\gamma _p^{(tr)}`$.

At this stage we have the equation for the fractions (10) and Eqs. (17) for the angular distribution functions. It is now our task to describe the temporal evolution of photoinduced anisotropy in terms of the averaged components of the order parameter tensor de Gennes and Prost (1993)

$$S_{ij}(\widehat{𝐧})=2^1(3n_in_j\delta _{ij}).$$
(18)
The simplest case occurs for the order parameters of *cis* molecules. Integrating Eq. (17a) multiplied by $`S_{ij}(\widehat{𝐧})`$ over angles gives the following result:

$$\frac{S_{ij}^{(cis)}}{t}=n_{tr}P_{tr}_{tr}S_{ij}^{(cis)},$$
(19)
where $`S_{ij}^{(\alpha )}S_{ij}(\widehat{𝐧})_\alpha `$. Rotational diffusion of *cis* molecules can be taken into account by replacing the coefficient on the right hand side of Eq. (19) with $`n_{tr}P_{tr}_{tr}+6D_r`$, where $`D_r`$ is the rotational diffusion constant. In any case, ordering kinetics of *cis* molecules is irrelevant provided the subsystem of *cis* groups is initially isotropic. The reason is that photo-isomerization does not make angular distribution of *cis* fragments anisotropic in our model.

We can now multiply Eqs. (17b) and (17c) by $`S_{ij}(\widehat{𝐧})`$ and integrate the resulting equations over the angles to obtain the following system:

$`n_{tr}{\displaystyle \frac{S_{ij}^{(tr)}}{t}}=2/3q_tIun_{tr}G_{ij;xx}^{(tr)}n_{cis}`$
$`\times (\gamma _c+q_cI)S_{ij}^{(tr)}+\gamma _{tr}n_{tr}(S_{ij}^{(p)}S_{ij}^{(tr)}),`$ (20a)
$`{\displaystyle \frac{S_{ij}^{(p)}}{t}}=\gamma _pn_{tr}(S_{ij}^{(p)}S_{ij}^{(tr)}),`$ (20b)
where $`G_{ij;mn}^{(\alpha )}`$ is the order parameter correlation function (correlator) defined as follows:

$$G_{ij;mn}^{(\alpha )}=S_{ij}(\widehat{𝐧})S_{mn}(\widehat{𝐧})_\alpha S_{ij}^{(\alpha )}S_{mn}^{(\alpha )}.$$
(21)
These functions characterize response of the side groups to the pumping light.

Eqs. (20) will give the system for the components of the order parameter tensor, if a closure can be found linking the correlation functions and $`S_{ij}^{(\alpha )}`$. The simplest closure can be obtained by writing the products of the order parameter components as a sum of spherical harmonics and neglecting the high order harmonics. In particular, applying this procedure to the diagonal order parameter components gives the following parabolic approximation for the order parameter autocorrelators Yaroshchuk et al. (2001c)

$$G_{ii;ii}^{(tr)}1/5+2/7S_{ii}_{tr}S_{ii}_{tr}^2.$$
(22)
According to the definition (21), the autocorrelators $`G_{ii;ii}^{(tr)}`$ must be non-negative. From the other hand, the values of $`S_{ii}_{tr}`$ are ranged from $`0.5`$ to $`1`$ de Gennes and Prost (1993) and the expression on the right hand side of Eq. (22) takes negative values on the specified interval. In order to restore the correct behavior, we need to modify the approximation (22). Our assumption is that it can be done by rescaling the order parameter components: $`S_{ii}_{tr}\lambda S_{ii}_{tr}`$, where $`\lambda `$ is the coefficient that takes into account contributions coming from the high order harmonics. In our calculations we used the largest value of $`\lambda `$, $`\lambda _{max}=(1+0.6\sqrt{30})/7`$. This implies that there are no fluctuations provided the molecules are perfectly aligned along the coordinate unit vector $`\widehat{𝐞}_i`$ and $`G_{ii;ii}^{(tr)}=0`$ at $`S_{ii}_{tr}=1`$.

By using the modified parabolic approximation for the correlators, we can now write down the resulting system for the diagonal components of the order parameter tensor in the final form:

$`n_{tr}{\displaystyle \frac{S}{t}}=2u/3q_tI(5/7+2\lambda /7S\lambda ^2S^2)n_{tr}`$
$`(\gamma _c+q_cI)n_{cis}S+\gamma _{tr}n_{tr}(S_pS),`$ (23)
$`n_{tr}{\displaystyle \frac{\mathrm{\Delta }S}{t}}=2u/3q_tI\lambda (2/7+\lambda S)n_{tr}\mathrm{\Delta }Sn_{cis}`$
$`\times (\gamma _c+q_cI)\mathrm{\Delta }S+\gamma _{tr}n_{tr}(\mathrm{\Delta }S_p\mathrm{\Delta }S),`$ (24)
$`{\displaystyle \frac{S_p}{t}}=\gamma _pn_{tr}(S_pS),`$ (25)
$`{\displaystyle \frac{\mathrm{\Delta }S_p}{t}}=\gamma _pn_{tr}(\mathrm{\Delta }S_p\mathrm{\Delta }S),`$ (26)
where $`SS_{xx}_{tr}`$, $`\mathrm{\Delta }SS_{yy}S_{zz}_{tr}`$, $`S_pS_{xx}_p`$ and $`\mathrm{\Delta }S_pS_{yy}S_{zz}_p`$.

## III Numerical results

In this section we demonstrate how our model can be employed to interpret the experimental data of the UV absorption measurements for different irradiation doses. For this purpose we will use the data obtained by Dr. O. Yaroshchuk and co-workers (Institute of Physics of NASU, Ukraine). Since the experimental procedure has been described in Ref. Yaroshchuk et al. (2001c) and a more comprehensive study is the subject of joint publication Yaroshchuk et al. , only a brief summary will be given below.

According to Ref. Yaroshchuk et al. (2001c), the normally incident pumping UV light used in the experiments is propagating along the $`z`$-axis and is linearly polarized with the polarization vector $`𝐄`$ parallel to the $`x`$-axis. The irradiation was provided in several steps followed by absorption measurements after the waiting time period taken to be longer than 15 min. These measurements were carried out to yield the optical density components $`D_x`$ and $`D_y`$ for the testing beam which is linearly polarized along the $`x`$ and $`y`$ axes, respectively. The wavelength of the testing light was tuned to the absorption maximum of azobenzene chromophores at $`\lambda _t=343`$ nm. The principal absorption coefficients $`D_i`$ can be related to the concentrations and the order parameters as follows

$`D_i\sigma _{ii}^{(tr)}_{tr}n_{tr}+\sigma ^{(cis)}n_{cis}`$
$`(1+u^{(a)}(2S_i+1)/3)n_{tr}+q_{ct}n_{cis},`$ (27)
where $`S_iS_{ii}_{tr}`$; $`u^{(a)}`$ is the absorption anisotropy parameter and $`q_{ct}`$ is the ratio of $`\sigma ^{(cis)}`$ and $`\sigma _{}^{(tr)}`$ at the wavelength of probing light.

The lifetime of the *cis* fragments was found to be much longer than the periods examined. So, we can safely take the limit of long-living *cis* molecules and neglect $`\gamma _c`$ in our calculations. In this case the photoselection mechanism discussed in Sec. I can be thought to dominate the process of photo-reorientation. There are, however, two sets of experimental data measured at two different wavelengths of the pumping UV light: $`\lambda _{ex}=488`$ nm and $`\lambda _{ex}=365`$ nm. These data are shown in Fig. 1a and Fig. 2a, respectively.

Fig. 1a presents the case in which the wavelength of light is far from the absorption maximum and dependencies of the absorption coefficients $`D_x`$ and $`D_y`$ on the irradiation time are typical of photoorientation mechanism. In this case the fraction of *cis* molecules is negligible and a sum of all the principal absorption coefficients, $`D_{tot}=D_x+D_y+D_z`$, does not depend on irradiation doses. For the photosteady state, where $`D_y^{(st)}=D_z^{(st)}`$, this will yield the relation

$$D_{tot}=D_x^{(st)}+2D_y^{(st)}=D_x+D_y+D_z.$$
(28)
The absorption component $`D_z`$ depicted in Fig. 1a was estimated by using Eq. (28). In addition, Fig. 1b shows the absorption order parameters $`S_i^{(a)}`$ computed from the expression

$$S_i^{(a)}=\frac{2D_iD_jD_k}{2(D_x+D_y+D_z)},ijk.$$
(29)
From Eq. (27) with $`n_{cis}0`$ these order parameters are proportional to $`S_i`$: $`S_i^{(a)}=u^{(a)}/(3+u^{(a)})S_i`$.

By contrast, referring to Fig. 2a, it is seen that both experimental dependencies $`D_x`$ and $`D_y`$ are decreasing functions of the irradiation time under the wavelength is near the maximum of absorption band with $`\lambda _{ex}=365`$ nm. It indicates that in this case POA is governed by the mechanism of photoselection. So, we have the process of photo-reorientation characterized by two different mechanisms depending on the wavelength of pumping light.

In order to characterize the regime of POA, we can use the fraction of *cis* fragments in the photo-stationary state. From Eq. (10) this fraction is given by

$$n_{cis}^{(st)}=\frac{3+u(1+2S_{st})}{3(r+1)+u(1+2S_{st})},$$
(30)
where $`r(\gamma _c+q_cI)/(q_tI)`$, $`S_{st}S_x^{(st)}`$ and the corresponding value of the order parameter is a solution of the following equation

$`2u(1/5+2\lambda /7S_{st}\lambda ^2S_{st}^{\mathrm{\hspace{0.17em}2}})`$
$`=S_{st}(3+u(1+2S_{st})),`$ (31)
deduced by using Eqs. (23) and (25).

When $`\gamma _c=0`$, the parameter $`r`$ in Eq. (30) is the ratio of $`q_c`$ and $`q_t`$. At small values of $`r`$ it will yield the fraction $`n_{cis}^{(st)}`$ that is close to the unity and we have the kinetics of POA in the regime of photoselection. In the opposite case of sufficiently large values of $`r`$ the photosteady fraction of *cis* molecules will be very small that is typical of the photoorientation mechanism. This effect is demonstrated in Figs. 1 and 2. The figures show theoretical curves computed at different values of $`r`$: $`60.0`$ and $`0.1`$, respectively. From Eqs. (30) and (31) the corresponding fractions of *cis* fragments in the photostationary state can be estimated at about $`0.02`$ and $`0.96`$.

The theoretical curves are computed by solving the rate equations deduced in the previous section. Initial values of the order parameters $`S(0)`$ and $`\mathrm{\Delta }S(0)`$ are taken from the experimental data measured at $`\lambda _{ex}=488`$ nm. Since the system is initially at the equilibrium state, the remaining part of the initial conditions is: $`S_p(0)=S(0)`$, $`\mathrm{\Delta }S_p(0)=\mathrm{\Delta }S(0)`$, $`n_{tr}(0)=1`$ and $`n_{cis}(0)=0`$.

Numerical calculations in the presence of irradiation were followed by computing the stationary values of $`S`$ and $`\mathrm{\Delta }S`$ to which the order parameters decay after switching off the irradiation at time $`t`$. The experimental estimate for the relaxation time characterizing decay of $`D_i(t)`$ to its stationary value after switching off the irradiation is about 1 h. The theoretical value of this relaxation time, deduced from solution of the kinetic equations in the absence of irradiation, is $`1/(\gamma _p+\gamma _{tr})`$. So, in the simplest case, we can assume both relaxation times, $`\tau _p`$ ($`\gamma _p=1/\tau _p`$) and $`\tau _{tr}`$ ($`\gamma _{tr}=1/\tau _{tr}`$), to be equal 120 min.

There are a number of additional photochemical parameters that enter the model and are listed in Table 1. The table shows the estimates for absorption cross section of *cis* molecules $`\sigma ^{(cis)}`$ and average absorption cross section of *trans* fragments, $`\sigma ^{(tr)}=(\sigma _{||}^{(tr)}+2\sigma _{}^{(tr)})/3`$, obtained from the UV spectra of the polymer solved in toluene. We shall omit details on the method of evaluation which is briefly described in Ref. Yaroshchuk et al. (2001c).

For this polymer the absorption anisotropy parameters and the quantum efficiencies are unknown and need to be fitted. We used the value of $`S_{st}`$ as an adjustable parameter, so that the anisotropy parameters $`u`$ and $`u^{(a)}`$ can be derived from Eq. (31) and from the experimental value of the absorption order parameter $`S_{st}^{(a)}`$ measured at $`\lambda _{ex}=488`$ nm in the photosteady state. The numerical results presented in Figs. 1 and 2 are computed at $`u^{(a)}=11.0`$ and $`q_{ct}=2.15`$. Note that the quantum efficiencies are of the same order of magnitude as the experimental values for other azobenzene compounds Mita et al. (1989).

## IV Discussion

Despite our theoretical considerations are rather phenomenological they emphasize the key points that should be addressed by such kind of theories. These are the angular redistribution probabilities and the order parameter correlation functions. The redistribution operators, in particular, define how the system relaxes after switching off the irradiation and can serve to introduce self-consistent fields. The correlators describe response of *trans* molecules to the exciting light and determine the properties of the photosaturated state.

Our simple model relies on the assumption that the *cis* fragments are isotropic and do not affect the ordering kinetics directly. By contrast to the mean field models of Refs. Pederson and Michael (1997); Pederson et al. (1998); Sajti et al. (2001), it implies that the presence of long-living angular correlations is irrelevant for *cis* molecules. Certainly, this is the simplest case to start from before studying more complicated models. The model depends on a few parameters that enter the equations and that can be estimated from the experimental data. Only the absorption anisotropy parameters and the quantum yields need to be adjusted.

After making comparison between the experimental data and the theoretical results we can conclude that the theory correctly captures the basic features of POA in azopolymers. It predicts that in the limit of long-living *cis* fragments the regime of POA will be governed by the parameter $`r`$ which is the ratio of $`\mathrm{\Phi }_{cistrans}\sigma ^{(cis)}`$ and $`\mathrm{\Phi }_{transcis}\sigma _{}^{(tr)}`$.

For large values of $`r`$ the fraction of *cis* molecules in the photosaturated state is negligible and dependencies of the principal absorption coefficients on illumination doses are typical for the kinetics in the regime of photoorientation. It means that the $`\text{cis}\text{trans}`$ transitions stimulated by the exciting light will efficiently deplete the *cis* state and the absorption coefficients are controlled by the terms proportional to the order parameter of *trans* molecules (see Eq. (27)).

By contrast, if the value of $`r`$ is sufficiently small, there is nothing to prevent the *cis* state from being populated under the action of UV light and the fraction of *cis* molecules approaches the unity upon illumination. In this case the contribution of *trans* isomers to the absorbance becomes negligible as the illumination dose increases and we have the kinetics of POA dominated by the photoselection mechanism.

We have thus demonstrated that the predictions of the theory are in accord with the experimental data, where the difference in the photochemical parameters at $`\lambda _{ex}=365`$ nm and $`\lambda _{ex}=488`$ nm can be attributed to the interplay between $`\pi \pi ^{}`$ and n$`\pi ^{}`$ transitions of the azobenzene moieties. Our findings confirm the conclusion that the dependence of photoisomerization rate on molecular axes orientation (see Eqs. (6) and (7)) plays a leading part in the process of photo-reorientation.

Our concluding remark concerns an overall strategy used throughout this paper. We have analyzed the general structure of phenomenological models to find out how the models incorporate different physical assumptions. Then we studied the simple model and compared the results of calculations with the experimental data. Recently we have applied this strategy to describe the photoorientation regime of POA in the polymer, where the out-of-plane reorientation of the dye molecules is suppressed Yaroshchuk et al. (2001c). Since the method is found to be applicable to the different regimes of POA, we have a useful tool for studying photoinduced ordering processes in azopolymers. But, not speaking of the parabolic approximation for the correlators, even the very possibility to describe the kinetics in terms of one-particle distribution functions needs to be justified by a more detailed theory. The structure of models is likely to be recovered in the mean field approximation Chaikin and Lubensky (1995) and we hope that this work will stimulate further progress in this direction.

###### Acknowledgements.

We are grateful to Dr. O. Yaroshchuk (Institute of Physics of NASU, Ukraine) for stimulating discussions and his kind permission to use the experimental data.