Effects of different initial condition samplings on photodynamics and spectrum of pyrrole

摘要: Semiclassical simulations of spectrum and dynamics complex molecules require statistical sampling coordinates momenta. The effects using thermal quantum samplings are analyzed taking pyrrole as a test case. It is shown that there significant differences in the results obtained with each these two approaches. Overall, based on Wigner distribution renders superior results, comparing well to experiments. Dynamics surface hopping ADC(2) reveal internal conversion ground state occurs not only through H-elimination path, but also ring-distortion paths, which have been systematically neglected by diverse experimental setups. analysis reaction paths shows ionization potential varies more than 5 eV between excited at Franck-Condon region intersections state. This feature may major implications for time-resolved photoelectron spectroscopy. (c) 2015 Wiley Periodicals, Inc.