In this paper we present the theory and implementation of the symmetry-adapted cluster (SAC) and symmetry-adapted cluster-configuration interaction (SAC-CI) method, including the solvent effect, using the polarizable continuum model (PCM). The PCM and SAC/SAC-CI were consistently combined in terms of the energy functional formalism. The excitation energies were calculated by means of the state-specific approach, the advantage of which over the linear-response approach has been shown. The single-point energy calculation and its analytical energy derivatives are presented and implemented, where the free-energy and its derivatives are evaluated because of the presence of solute-solvent interactions. We have applied this method to s-trans-acrolein and metylenecyclopropene of their electronic excitation in solution. The molecular geometries in the ground and excited states were optimized in vacuum and in solution, and both the vertical and adiabatic excitations were studied. The PCM-SAC/SAC-CI reproduced the known trend of the solvent effect on the vertical excitation energies but the shift values were underestimated. The excited state geometry in planar and nonplanar conformations was investigated. The importance of using state-specific methods was shown for the solvent effect on the optimized geometry in the excited state. The mechanism of the solvent effect is discussed in terms of the Mulliken charges and electronic dipole moment.
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14 July 2010
Research Article|
July 13 2010
Symmetry-adapted cluster and symmetry-adapted cluster-configuration interaction method in the polarizable continuum model: Theory of the solvent effect on the electronic excitation of molecules in solution
Roberto Cammi;
Roberto Cammi
a)
1Dipartmento di Chimica,
Università di Parma
, Viale delle Scienze 17/A, 43100 Parma, Italy
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Ryoichi Fukuda;
Ryoichi Fukuda
b)
2Department of Theoretical and Computational Molecular Science,
Institute for Molecular Science and Research Center for Computational Science
, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Japan
3Japan Science and Technology Agency,
CREST
, Sanboncho-5, Chiyoda-ku, Tokyo 102-0075, Japan
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Masahiro Ehara;
Masahiro Ehara
c)
2Department of Theoretical and Computational Molecular Science,
Institute for Molecular Science and Research Center for Computational Science
, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585, Japan
3Japan Science and Technology Agency,
CREST
, Sanboncho-5, Chiyoda-ku, Tokyo 102-0075, Japan
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Hiroshi Nakatsuji
Hiroshi Nakatsuji
d)
3Japan Science and Technology Agency,
CREST
, Sanboncho-5, Chiyoda-ku, Tokyo 102-0075, Japan
4
Quantum Chemistry Research Institute
, Kyodai Katsura Venture Plaza, 1-36 Goryo Oohara, Nishikyo-ku, Kyoto 615-8245, Japan
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a)
Electronic mail: chifi@unipr.it.
b)
Electronic mail: fukuda@ims.ac.jp.
c)
Electronic mail: ehara@ims.ac.jp.
d)
Electronic mail: h.nakatsuji@qcri.or.jp.
J. Chem. Phys. 133, 024104 (2010)
Article history
Received:
March 30 2010
Accepted:
June 02 2010
Citation
Roberto Cammi, Ryoichi Fukuda, Masahiro Ehara, Hiroshi Nakatsuji; Symmetry-adapted cluster and symmetry-adapted cluster-configuration interaction method in the polarizable continuum model: Theory of the solvent effect on the electronic excitation of molecules in solution. J. Chem. Phys. 14 July 2010; 133 (2): 024104. https://doi.org/10.1063/1.3456540
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