Ab initio molecular orbital studies on the structure, energies, and photodissociation of the electronic excited states of c2h
J. Chem. Phys., 108 (2):
626--636 (1998)Abstract
High level ab initio calculations have been carried out to study seven electronic states of C2H. The calculated equilibrium structure, energetics and vibrational frequencies for the 3 (2)A' state at the CASPT2/PVTZ level are in good agreement with those obtained experimentally by Hsu ct al. The transition dipole moments from the ground state C2H to electronic excited states depend sensitively on the H-C-C bending angle and often peak at nonlinear configurations. Based on this and the dissociation behavior of the excited states, we predict A (1) Pi(u) and c (3) Sigma(u)(+) C-2 fragments to be rich in population, the former of which is experimentally detected recently by Jackson er al. The ground X (1) Sigma(g)(+) and the a (3) Pi(u) state C-2 are expected to be formed via the nonadiabatic process 3 (2)A'-->2 (2)A' or 4 (2)A'-->3 (2)A'-->2 (2)A', which is in accord with the experimentally observed lifetime pattern by Hsu er al. No reverse barrier for CC-H dissociation was found on the X and A electronic states of C2H in the linear configuration. The 2 (2)A' state, however, develops a distinct "barrier" (not a true saddle point) along dissociation coordinate when the H-C-C is significantly bent, due to the interaction with upper electronic state. Since the 2 (2)A' state energetically prefers a linear dissociation, we suspect that the upper bound of the CC-H bond energy measured by Hsu ct ill. is not severally affected by this "barrier." (C) 1998 American Institute of Physics.