A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan (Russia), Fax: (+7) 843-273-22-53.
Chemphyschem. 2012 Dec 21;13(18):4186-94. doi: 10.1002/cphc.201200641. Epub 2012 Nov 26.
An analytical approach aimed at modeling the nonlinear optical (NLO) response of a polymer electret with incorporated organic dipole chromophores is extended to the dynamic case. The approach allows the effect of the locally anisotropic, polarizable, deformable polymer matrix on the chromophore NLO response to be accounted for. The method exploits the original cavity ansatz according to which the virtual cavity occupied by the chromophore in the polymer matrix is chosen to be conformal to the characteristic ellipsoid of the generalized permittivity tensor. Analytical expressions for the dynamic electric moments of dipole chromophores and macroscopic polarization of a polymer electret at fundamental and second harmonic frequencies are obtained by using a computational scheme based on two self-consistency procedures. On the basis of the expressions for dynamic macroscopic polarization, the analytical formulas for linear, chi(j)(i(1)) (omega), and quadratic, chi(jk)(i(2)) (2omega), electric susceptibilities are obtained. The presented expressions establish the relationship between the molecular polarizabilities of chromophores and the macroscopic electrical properties of the polymer electret.
一种旨在对具有掺入有机偶极子生色团的聚合物驻极体的非线性光学（NLO）响应进行建模的分析方法被扩展到动态情况。该方法允许考虑聚合物基质的局部各向异性、极化和可变形对生色团 NLO 响应的影响。该方法利用原始腔假设，根据该假设，生色团在聚合物基质中占据的虚拟腔被选择为与广义介电张量的特征椭球共形。通过使用基于两个自洽程序的计算方案，获得了在基频和二次谐波频率下偶极生色团的动态电矩和聚合物驻极体的宏观极化的解析表达式。基于动态宏观极化的表达式，得到了线性、chi(j)(i(1)) (omega) 和二次、chi(jk)(i(2)) (2omega) 电感应的解析公式。所提出的表达式建立了生色团的分子极化率与聚合物驻极体的宏观电性质之间的关系。
