The primary step of the photodissociation in CH3N0 and NH2NO has been investigated by ab initio SCF-CI techniques. The first singlet excited state presents a barrier along the dissociation coordinate both for CH3N0 and for the planar form of NH2N0. However, NH2N0 prefers a twisted and pyramidalized structure in SI, with no barrier to dissociation. These features of the SI surface explain the observation of a vibrational structure in the n - T* spectrum of (CH3)2NN0, dominate the dissociation mechanism (vibrational predissociation vs. intersystem crossing or internal conversion), and may influence the quantum yields in the condensed phase.
Ab initio study of the photodissociation of nitrosoalkanes and nitrosamines
CIMIRAGLIA, Renzo;
1985
Abstract
The primary step of the photodissociation in CH3N0 and NH2NO has been investigated by ab initio SCF-CI techniques. The first singlet excited state presents a barrier along the dissociation coordinate both for CH3N0 and for the planar form of NH2N0. However, NH2N0 prefers a twisted and pyramidalized structure in SI, with no barrier to dissociation. These features of the SI surface explain the observation of a vibrational structure in the n - T* spectrum of (CH3)2NN0, dominate the dissociation mechanism (vibrational predissociation vs. intersystem crossing or internal conversion), and may influence the quantum yields in the condensed phase.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
