Photodynamics of azomethane: a nonadiabatic surface-hopping study.
The internal conversion and hot ground-state dynamics of trans- and cis-azomethane starting in the S(1) state have been investigated by nonadiabatic ab initio surface hopping dynamics using MCSCF-GVB-CAS and MRCISD methods and by determining energy minima and saddle points, minima on the crossing seam, and minimum energy pathways on the ground and first excited-state surfaces. The lifetimes and photoproducts from the dynamics simulations, geometric properties, excitation energies of selected stationary points and minimum energy pathways between them are reported. Our results favor a statistical model with trans-AZM moving to the ground-state minima before the first CN dissociation takes place. A detailed discussion in comparison to recent experimental and theoretical data is presented.
Sellner
Bernhard
B
Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, A 1090 Vienna, Austria.
Ruckenbauer
Matthias
M
Stambolić
Ivan
I
Barbatti
Mario
M
Aquino
Adelia J A
AJ
Lischka
Hans
H
D001391:Azo Compounds / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D010777:Photochemistry; D011789:Quantum Theory; D013237:Stereoisomerism
D001391:Azo Compounds; C001825:azomethane