Analytical solutions for the dynamic Kerr effect: Linear response of polar and polarizable molecules to a weak ac electric field superimposed on a strong dc bias field
| Autor: | Pierre-Michel Déjardin, J. L. Déjardin, Yu. P. Kalmykov |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 107:508-523 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.474412 |
| Popis: | The infinite hierarchy of differential-recurrence relations for ensemble averages of the spherical harmonics pertaining to the noninertial rotational Brownian motion of an ensemble of polar and anisotropically polarizable molecules in a strong external dc electric field is derived by averaging the underlying Langevin equation. This procedure avoids recourse to the Fokker–Planck equation, the solution of which involves complicated mathematical manipulations. By calculating the Laplace transforms of the relaxation functions for the dynamic Kerr effect of symmetric top molecules, two equilibrium correlation functions are established, thus allowing one to express the corresponding birefringence ac responses by using linear response theory. Exact analytic solutions for the spectra of these correlation functions and relaxation times are first calculated for two limiting cases, namely, pure induced dipole moments and pure permanent moments, using the continued fraction method. The general case where both types o... |
| Databáze: | OpenAIRE |
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