Abstract
The vibronic absorption spectrum of the electric dipole forbidden and vibronically allowed S1(1 A2) ← S0(1 A1) transition of formaldehyde is calculated by Gaussian wavepacket and semiclassical methods, along with numerically exact reference calculations, using the potential energy surface of Fu, Shepler, and Bowman ( J. Am. Chem. Soc. 2011, 133, 7957). Specifically, the variational multiconfigurational Gaussian (vMCG) approach and the Herman-Kluk semiclassical initial value representation (HK-SCIVR) are compared to assess the accuracy and convergence of these methods, benchmarked against numerically exact time-dependent wavepacket propagation (TDWP) on the reference potential energy surface. The vMCG calculation is shown to converge quite well with about 100 variationally evolving Gaussian functions and using a local cubic expansion instead of the conventional local harmonic approximation. By contrast, the HK-SCIVR approach with ∼105 trajectories reproduces the vibrationally structured spectral envelope correctly but yields a strongly broadened spectrum. The comparison of the computed absorption spectrum with experiment shows that the relevant vibronic progressions are reasonably reproduced by all computations, but deviations o...Continue Reading
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