Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States
We report multistate trajectory simulations, including coherence, decoherence, and multidimensional tunneling, of phenol photodissociation dynamics. The calculations are based on full-dimensional anchor-points reactive potential surfaces and state couplings fit to electronic structure calculations including dynamical correlation with an augmented correlation-consistent polarized valence double-ζ basis set. The calculations successfully reproduce the experimentally observed bimodal character of the total kinetic energy release spectra and confirm the interpretation of the most recent experiments that the photodissociation process is dominated by tunneling. Analysis of the trajectories uncovers an unexpected dissociation pathway for one quantum excitation of the O–H stretching mode of the S1 state, namely, tunneling in a coherent mixture of states starting in a smaller ROH (~0.9–1.0 Å) region than has previously been invoked. The simulations also show that most trajectories do not pass close to the S1–S2 conical intersection (they have a minimum gap greater than 0.6 eV), they provide statistics on the out-of-plane angles at the locations of the minimum energy adiabatic gap, and they reveal information about which vibrational modes are most highly activated in the products.
- Research Organization:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0008666
- OSTI ID:
- 1201858
- Alternate ID(s):
- OSTI ID: 1455128
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 136 Journal Issue: 46; ISSN 0002-7863
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Similar Records
Mixed quantum/classical investigation of the photodissociation of NH{sub 3}(A-tilde) and a practical method for maintaining zero-point energy in classical trajectories
Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory