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Contemporary Research: Theory
Influence of the active space on CASSCF nonadiabatic dynamics simulations
Article first published online: 18 JAN 2011
DOI: 10.1002/qua.22978
Copyright © 2011 Wiley Periodicals, Inc.
Issue
International Journal of Quantum Chemistry
Special Issue: A Celebration of the Scientific Achievements of Björn O. Roos
Volume 111, Issue 13, pages 3307–3315, 5 November 2011
Additional Information
How to Cite
Szymczak, J. J., Barbatti, M. and Lischka, H. (2011), Influence of the active space on CASSCF nonadiabatic dynamics simulations. International Journal of Quantum Chemistry, 111: 3307–3315. doi: 10.1002/qua.22978
Publication History
- Issue published online: 25 JUL 2011
- Article first published online: 18 JAN 2011
- Manuscript Accepted: 4 OCT 2010
- Manuscript Received: 14 SEP 2010
Funded by
- Austrian Science Fund [Special Research Programs F16 (Advanced Light Sources) and F41 (ViCoM) and Project P18411-N19]
- Vienna Scientific Cluster [projects 70019 and 70151]
- Abstract
- Article
- References
- Cited By
Keywords:
- dynamics;
- excited states;
- active space;
- reaction path;
- conical intersection
Abstract
Nonadiabatic dynamics simulations are performed at four different extended ab initio CASSCF levels for 4-aminopyrimidine, which had been selected because of its structural relationship to DNA nucleobases, aiming at the assessment of the influence of the active space composition on the qualitative and quantitative dynamics predictions. Reaction pathways connecting the Franck-Condon region to the three main regions of the conical intersection seam were also computed at the same four levels and also using the CASPT2 method. The results show that the theoretical approach has significant influence on quantitative aspects of the dynamics. Nevertheless, relatively uniform qualitative predictions are obtained independently of the CAS level. A well-balanced treatment of lone-pair orbitals in the active space was shown to be a key factor for the reliability of the results. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111:3307–3315, 2011