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Modeling irreversible molecular internal conversion using the time-dependent variational approach with sD2 ansatz†
Mantas Jakučionis,Tomas Mancal,Darius Abramavičius
Physical Chemistry Chemical Physics Pub Date : 04/01/2020 00:00:00 , DOI:10.1039/D0CP01092H
Abstract

Effects of non-linear coupling between the system and the bath vibrational modes on the system internal conversion dynamics are investigated using the Dirac–Frenkel variational approach with a newly defined sD2 ansatz. It explicitly accounts for the entangled system electron-vibrational states, while the bath quantum harmonic oscillator states are expanded in a superposition of quantum coherent states. Using a non-adiabatically coupled three-level model, we show that efficient irreversible internal conversion due to quadratic vibrational-bath coupling occurs when the initially populated system vibrational levels are in resonance with the vibrational levels of a lower energy electronic state, also, a non-Gaussian bath wavepacket representation is required. The quadratic system-bath couplings result in broadened and asymmetrically squeezed bath quantum harmonic oscillator wavepackets in the coordinate-momentum phase space.

Graphical abstract: Modeling irreversible molecular internal conversion using the time-dependent variational approach with sD2 ansatz
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