title: Rotationally resolved optical rotation and circular dichroism effects for symmetric top molecules induced by a resonant circularly polarized pumping optical field.
abstract: The rotationally resolved laser-induced optical activity including the laser-induced optical rotation (LIOR) and laser-induced circular dichroism (LICD) effects of an IR probing light pumped by a collinear intense resonant circularly polarized light dependent on the third-order susceptibility due to the pure electric dipole interaction for achiral symmetric top molecules in the gas phase is discussed theoretically. The laser-induced optical activity contains four distinct contributions named A, B, C, and D terms: the B term of the LIOR and LICD arising from the rotational wave function perturbed by the pumping light is deduced using the semiclassical perturbation theory, and the expressions for A, C, and D terms, respectively, due to the ac Stark effect, the Boltzmann statistical redistribution, and the alteration of occupation polability, are obtained from previous results [Zheng, R.-H.; Chen, D.-M.; Wei, W.-M.; He, T.-J.; Liu, F.-C. J. Chem. Phys. 2004, 121, 6835]. The microwave-IR double resonant spectrum is proposed to detect the LIOR and LICD effects. As an example, the LIOR and LICD for the HCF(3) molecules in the conditions of 298.15 K and 0.3 Torr when the IR probing light sweeps over the rotational-vibrational transition of the v(5) and v(1) modes and the right circularly polarized microwave pumping light with the intensity of 1 kW cm(-2) at the resonant frequency 40.84 GHz are calculated on the basis of the B3LYP/6-311++G* computations. The theoretical results indicate that the B term can be of the same order of magnitude as the A and D terms, and the LIOR and LICD can be measurable in comparison to the rotationally resolved MVCD. The laser-induced optical activity may provide useful new information and form a basis for a different kind of optical activity spectroscopy.
authors.affiliation: School of Life Science, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China. zrh@ustc.edu
authors.forename: Ren-Hui
authors.initials: RH
authors.lastname: Zheng
authors.forename: Wen-Mei
authors.initials: WM
authors.lastname: Wei
mesh_terms: D002942:Circular Dichroism / Q000379:methods*; D013237:Stereoisomerism