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Ab Initio Trajectory Surface-Hopping Study on Ultrafast Deactivation Process of Thiophene.
- Source :
-
Journal of Physical Chemistry A . Oct2011, Vol. 115 Issue 42, p11544-11550. 7p. - Publication Year :
- 2011
-
Abstract
- The ultrafast S1(¹ππ*)→ Sodeactivation process of thiophene in the gas phase has been simulated with the complete active space self-consistent field (CASSCF) based fewest switch surface hopping method. It was found that most of the calculated trajectories (~80%) decay to the ground state (So) with an averaged time constant of 65 ± 5 fs. This is in good agreement with the experimental value of about 80 fs. Two conical intersections were determined to be responsible for the ultrafast S1(¹ππ*)→ So internal conversion process. After thiophene is excited to the S1(¹ππ*) state in the Franck-Condon region, it quickly relaxes to the minimum of the S1(¹ππ*) state, then overcomes a small barrier near the conical intersection (CI(¹ππ*/¹πσ*)), and eventually arrives at the minimum of one C-S bond fission (S1(¹πσ*)). In the vicinity of this minimum, the conical intersection (CI(¹πσ*/So)) funnels the electron population to the ground state (So), completing the ultrafast S1(¹ππ*)→ So internal conversion process. This decay mechanism matches well with previous experimental and theoretical studies. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 10895639
- Volume :
- 115
- Issue :
- 42
- Database :
- Academic Search Index
- Journal :
- Journal of Physical Chemistry A
- Publication Type :
- Academic Journal
- Accession number :
- 69926457
- Full Text :
- https://doi.org/10.1021/jp206893n