TY  - JOUR
AU  - doMonte, S. A.
AU  - Dallos, M.
AU  - Müller, T.
AU  - Lischka, H.
TI  - MR-CISD and MR-AQCC calculation of excited states of Malonaldehyde: Geometry optimizations using analytical energy gradient methods and a systematic investigation of reference configuration sets
JO  - Collection of Czechoslovak chemical communications
VL  - 68
SN  - 0010-0765
CY  - Prague
PB  - Institute of Organic Chemistry and Biochemistry, Prague
M1  - PreJuSER-28420
SP  - 447 - 462
PY  - 2003
N1  - Record converted from VDB: 12.11.2012
AB  - Extended MR-CISD and MR-AQCC calculations have been performed on the ground state and the first two excited states of malonaldehyde. Full geometry optimizations have been carried for C-s and C-2v structures both at MR-CISD and MR-AQCC levels. Vertical and minimum-to-minimum excitation energies and oscillator strengths have been computed. Systematic studies have been undertaken concerning several types of reference spaces. Agreement with the experimental 0-0 transition energy to the S-1 state (expt. 3.50 eV, calc. 3.56 eV) and for the vertical excitation to S-2 (expt. band maximum 4.71 eV, best estimate 4.86 eV) is very good. In agreement with the CASSCF/CASPT2 results by Sobolewski and Domcke (J. Phys. Chem. A 1999, 103, 4494), we find that the hydrogen bond in malonaldehyde is weakened by excitation to the S-1 state. The barrier for proton transfer in the S-1 state is increased in comparison with the ground state.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000181709100002
DO  - DOI:10.1135/cccc20030447
UR  - https://juser.fz-juelich.de/record/28420
ER  -