Naslov
Study of the mechanism of the N−CO photodissociation in N, N-dimethylformamide by direct trajectory surface hopping simulations
(Study of the mechanism of the N-CO photodissociation in N, N-dimethylformamide by direct trajectory surface hopping simulations)

Autori
Eckert-Maksić, Mirjana ; Antol, Ivana

Izvornik
The Journal of Physical Chemistry A (1089-5639) 113 (2009), 45; 12582-12590

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
N; N-dimethylformamide; mechanism; photodissociation; dynamic simulations; on-the-fly surface-hopping

Sažetak
Photodynamics of N, N-dimethylformamide (DMF) in its low lying singlet excited nO-pi* and pi-pi* states have been explored by the direct trajectory surface-hopping method based on multiconfigurational ab initio calculations. The dynamics simulations starting in the first excited singlet state (nO-pi *) showed that in 57 % of trajectories S1 excited DMF decays to the ground via the crossing seam related to N-CO bond stretching MXS1. In 41% of all trajectories, the relaxation process on the S1 PES moves the molecule into minimum where it stays trapped till the end of simulation time. In simulations starting in the second excited state all of trajectories are found to deactivate through MXS5 (S2/S1) by very fast N-CO stretching. Since the N- CO dissociation process continues in the S1 potential energy surface, the most of the population overshoots the MXS1 and leads to fully dissociated electronically excited HCO and N(CH3)2 radicals. Mechanism for their deactivation by H-C- O and C-N-C bending modes is proposed.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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