화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.123, No.10, 1937-1944, 2019
Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3(2)A(3p(x)) Rydberg State: A Nine-Dimensional Quantum Study
The nonadiabatic predissociation dynamics of the hydroxymethyl radical (CH2OH) in its 3(2)A(3p(x)) state is investigated using a nine-dimensional quantum mechanical model based on an ab initio three coupled diabatic state potential energy matrix. The calculated absorption spectrum, which is dominated by predissociative resonances, is in excellent agreement with experiment. The predissociation is facilitated by two conical intersection seams formed between the 3(2)A(3p(x)) and 2(2)A(3s) states near the Franck-Condon region. The h and g vectors of energy minimized points on these seams are analyzed using the normal modes of the 3(2)A equilibrium structure. The low-lying predissociative resonances have been assigned and their lifetimes are less than 100 fs and moderately mode specific. The absorption spectrum is dominated by a CO vibrational progression, due apparently to the promotion of an electron from the ground state antibonding pi(co)* orbital to the carbon Rydberg orbital, which effectively increases the C-O bond order.