Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 20, Pages 4185-4190Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.6b02037
Keywords
-
Categories
Funding
- Department of Energy [DE-SC0008694]
- National Science Foundation (NSF) [CHE-0909227]
- NSF [CHE-1062891]
Ask authors/readers for more resources
The effect of nonadiabatic transitions on branching ratios, kinetic and internal energy distribution of fragments, and reaction mechanisms observed in acetaldehyde photodissociation is investigated by nonadiabatic molecular dynamics (NAMD) simulations using time-dependent hybrid density functional theory and Tully surface hopping. Homolytic bond breaking is approximately captured by allowing spin symmetry to break. The NAMD simulations reveal that nonadiabatic transitions selectively enhance the kinetic energy of certain internal degrees of freedom within approximately 50 fs. Branching ratios from NAMD and conventional hot Born-Oppenheimer molecular dynamics (BOMD) are similar and qualitatively agree with experiment. However, as opposed to the BOMD simulations, NAMD captures the high-energy tail of the experimental kinetic energy distribution. The extra kick of the nuclei in the direction of the nonadiabatic coupling vector results from nonadiabatic transitions close to conical intersections. From a mechanistic perspective, the nonadiabatic effects favor asynchronous over synchronous fragmentation and tend to suppress roaming.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available