Laser-polarization effects on coherent vibronic excitation of molecules with quasi-degenerate electronic states

Manabu Kanno, Yukari Ono, Hirohiko Kono, Yuichi Fujimura

研究成果: Article査読

21 被引用数 (Scopus)


The laser-polarization effects on nonadiabatically coupled π-electron rotation (ring current) and molecular vibration have been theoretically analyzed for aromatic molecules with quasi-degenerate excited states irradiated by an ultrashort laser pulse of arbitrary polarization. We first derived general formulations of the coherent electronic wave packet and expectation value of electronic angular momentum within a frozen-nuclei model. The relative quantum phase of the superposed quasi-degenerate states, which determines the oscillating behavior of angular momentum, can be manipulated by the ellipticity and orientation of the incident laser. Nuclear wave packet simulations with a model molecule confirmed the controllability of π-electron rotation, although the angular momentum is gradually reduced by nonadiabatic couplings. The amplitude of molecular vibration depends prominently on the orientation of linear polarization vectors rather than the helicity of circular polarization. The characteristic feature in vibrational amplitudes is attributed to the interference in nonadiabatic transition governed by the relative quantum phase between nuclear wave packets. This offers a new strategy for laser control of molecular vibrations through the wave packet interference in nonadiabatic transition.

ジャーナルJournal of Physical Chemistry A
出版ステータスPublished - 2012 11月 26

ASJC Scopus subject areas

  • 物理化学および理論化学


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