A Quantum Dynamics Study of cis- and trans-Stilbenes

Tuong Huynh\(^{1}\), Simon Neville\(^{2}\), and Michael Schuurman\(^{1,2}\)

\(^{1}\) University of Ottawa
\(^{2}\) National Research Council Canada

cis- and trans-Stilbene have a long-studied photochemistry arising from their photo-initiated isomerization process, in which the large-amplitude relative motion of the phenyl rings has led to the molecule being identified as a molecular switch. A quantitative description of the corresponding absorption spectrum would therefore be essential for a complete account of the ensuing dynamics. However, previous assignments of the absorption spectra for these molecules, which neglected the vibronic coupling effects, fail to properly characterize the spectra. We present here detailed analyses of the vibronic spectra of cis- and trans-stilbenes simulated from wavepacket propagation calculations using the multi-configuration time-dependent Hartree (MCTDH) method. To do so, vibronic coupling Hamiltonian models are constructed by direct fitting to diabatic potential matrices computed using the novel QD-DFT/MRCI(2) approach. Our simulated spectra reproduce the main features of the experimental spectra in solution. The role of intensity borrowing from transitions to ππ* states, and the excited state dynamics of each molecules, are also examined in our study.

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