A direct classical trajectory study of the acetone photodissociation on the triplet surface

• Type: Article in International Scientific Journal
• Date: 2003

Authors

Martinez Nunez, E (Author) Other; Fernandez Ramos, A (Author) Other; Cordeiro, MNDS (Author) FCUP; Vazquez, SA (Author) Other; Aoiz, FJ (Author) Other; Banares, L (Author) Other

Journal

Title: Journal of Chemical Physics

Vol. 119

Pages: 10618-10625

ISSN: 0021-9606

Publisher: American Institute of Physics

Indexing

ISI Web of Knowledge - 13 Citations

Scopus - 13 Citations

Scientific classification

FOS: Natural sciences > Physical sciences

Other information

Authenticus ID: P-000-EE2

DOI: 10.1063/1.1622387

Abstract (EN): Product energy distributions (PEDs) for the photodissociation of acetone at 266, 248, and 193 nm were evaluated by direct classical trajectory calculations on the lowest triplet potential energy surface. CASSCF(8,7) and MRCI+Q calculations were first performed to obtain a set of high-level ab initio data with which the semiempirical parameters were refined. The trajectories were initiated at the barrier, using two different microcanonical sampling methods. The results obtained for the excess energies corresponding to excitation at 266 and 248 nm are in good agreement with the experimental product energy partitioning, supporting a dissociation event taking place on the T-1 surface after intersystem crossing from the initially exited S-1 state. At 193 nm, the results obtained with the two sampling methods show significant discrepancies. The PEDs calculated with the anharmonic sampling procedure appear to be consistent with the experimental data. (C) 2003 American Institute of Physics.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 8