Predominance of Nonequilibrium Dynamics in the Photodissociation of Ketene in the Triplet State

Autor:	Keiji Morokuma, Alexey L. Kaledin, Jeonghee Seong
Rok vydání:	2001
Předmět:	chemistry.chemical_compound chemistry Field (physics) Phase space Photodissociation Potential energy surface Degrees of freedom (physics and chemistry) Ketene Complete active space Physical and Theoretical Chemistry Triplet state Atomic physics
Zdroj:	The Journal of Physical Chemistry A. 105:2731-2737
ISSN:	1520-5215 1089-5639
Popis:	The photodissociation of ketene is studied using direct surface-hopping classical trajectories where the energy and gradient are computed on the fly by means of state-averaged complete active space self-consistent field with a double-ζ polarized basis set. Three low-lying electronic states, singlets S0 and S1 and triplet T1, are involved in the process of photodissociation of triplet state ketene. We propagated a trajectory, starting at the Franck−Condon geometry on S1, and branched it out into many child trajectories every time the propagating potential energy surface (PES) crossed with another PES. The major photodissociation pathway to the triplet products was found to be S1 → S0 → T1 → CH2(X3B1) + CO(X1Σ+). It has been found that (1) the S0−T1 nonadiabatic transition creates the T1 species nonstatistically at restricted regions of phase space and (2) a large fraction of the T1 species thus created dissociates almost immediately, leaving no time for equilibration of internal degrees of freedom. Whether...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::56f50e7d798852b7dec2c97251d22190 https://doi.org/10.1021/jp003794c Zobrazit plný text záznamu