Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene
Abstract
The nonadiabatic photodynamics of s-trans-butadiene in its lowest singlet excited states is studied theoretically, using a fully quantal approach. The coupled 1B(u) and 2A(g) states are considered in the calculation, representing the lowest dipole-allowed electronic transition, and the dipole-forbidden state with substantial double-excitation character, respectively. Up to six nuclear degrees of freedom, including out-of-plane dihedral angles, are included. The calculation of the underlying potential energy surfaces relies on the CASPT2 method, where widely different CAS spaces have been compared. The ultrafast electronic population decay is confirmed, proceeding on a time scale of 30-40 fs. Pronounced out-of-plane distortions are obtained for the first time from fully quantal calculations. The complexity of the electronic absorption spectrum increases substantially upon including additional vibrational modes in the calculation. Further computations were performed to facilitate inclusi...on of the coupling to the ground state in subsequent work.
Source:
Journal of Physical Chemistry A, 2013, 117, 36, 8782-8793Publisher:
- American Chemical Society (ACS)
Funding / projects:
- Deutsche Forschungsgemeinschaft
- The study of physicochemical and biochemical processes in living environment that have impacts on pollution and the investigation of possibilities for minimizing the consequences (RS-172001)
DOI: 10.1021/jp404340m
ISSN: 1089-5639
PubMed: 23834412
WoS: 000330145400031
Scopus: 2-s2.0-84884334130
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Institution/Community
IHTMTY - JOUR AU - Komainda, A. AU - Ostojić, Bojana AU - Koeppel, H. PY - 2013 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1240 AB - The nonadiabatic photodynamics of s-trans-butadiene in its lowest singlet excited states is studied theoretically, using a fully quantal approach. The coupled 1B(u) and 2A(g) states are considered in the calculation, representing the lowest dipole-allowed electronic transition, and the dipole-forbidden state with substantial double-excitation character, respectively. Up to six nuclear degrees of freedom, including out-of-plane dihedral angles, are included. The calculation of the underlying potential energy surfaces relies on the CASPT2 method, where widely different CAS spaces have been compared. The ultrafast electronic population decay is confirmed, proceeding on a time scale of 30-40 fs. Pronounced out-of-plane distortions are obtained for the first time from fully quantal calculations. The complexity of the electronic absorption spectrum increases substantially upon including additional vibrational modes in the calculation. Further computations were performed to facilitate inclusion of the coupling to the ground state in subsequent work. PB - American Chemical Society (ACS) T2 - Journal of Physical Chemistry A T1 - Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene VL - 117 IS - 36 SP - 8782 EP - 8793 DO - 10.1021/jp404340m ER -
@article{ author = "Komainda, A. and Ostojić, Bojana and Koeppel, H.", year = "2013", abstract = "The nonadiabatic photodynamics of s-trans-butadiene in its lowest singlet excited states is studied theoretically, using a fully quantal approach. The coupled 1B(u) and 2A(g) states are considered in the calculation, representing the lowest dipole-allowed electronic transition, and the dipole-forbidden state with substantial double-excitation character, respectively. Up to six nuclear degrees of freedom, including out-of-plane dihedral angles, are included. The calculation of the underlying potential energy surfaces relies on the CASPT2 method, where widely different CAS spaces have been compared. The ultrafast electronic population decay is confirmed, proceeding on a time scale of 30-40 fs. Pronounced out-of-plane distortions are obtained for the first time from fully quantal calculations. The complexity of the electronic absorption spectrum increases substantially upon including additional vibrational modes in the calculation. Further computations were performed to facilitate inclusion of the coupling to the ground state in subsequent work.", publisher = "American Chemical Society (ACS)", journal = "Journal of Physical Chemistry A", title = "Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene", volume = "117", number = "36", pages = "8782-8793", doi = "10.1021/jp404340m" }
Komainda, A., Ostojić, B.,& Koeppel, H.. (2013). Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene. in Journal of Physical Chemistry A American Chemical Society (ACS)., 117(36), 8782-8793. https://doi.org/10.1021/jp404340m
Komainda A, Ostojić B, Koeppel H. Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene. in Journal of Physical Chemistry A. 2013;117(36):8782-8793. doi:10.1021/jp404340m .
Komainda, A., Ostojić, Bojana, Koeppel, H., "Ab Initio Quantum Study of Nonadiabatic S-1-S-2 Photodynamics of s-trans-Butadiene" in Journal of Physical Chemistry A, 117, no. 36 (2013):8782-8793, https://doi.org/10.1021/jp404340m . .