TY - JOUR
T1 - Structure and harmonic vibrational frequencies of cyclopentadiene in the lowest singlet states
AU - Kovář, Tomáš
AU - Lischka, Hans
N1 - Funding Information:
This work was sponsored by the Austrian “Fonds zur Forderung der Wissenschaftlichen Forschung”, Project No. P7979. The calculations were performed on the IBM ES/9021-720 of the computer center of the University of Vienna within the European Academic Supercomputer Initiative (EASI) sponsored by IBM. We are grateful for the ample supply of computer time.
PY - 1994/1/14
Y1 - 1994/1/14
N2 - MCSCF calculations are reported for the electronic ground state and the two lowest excited singlet states of cyclopentadiene. Molecular geometries have been optimized for each state individually and the complete harmonic force field calculated. Similar to the situation found for cis- and (trans-butadiene the CC double bond length significantly increases on electron excitation and the CC single bond length within the cis-butadiene substructure decreases. The changes in the vibrational frequencies and in the character of the vibrational modes on excitation is documented in detail. Whereas the electronic ground state and the 1 1B2 state have C2v symmetry (with the carbon ring system and the CH bonds in one plane) the 2 1A1 state is predicted to have a lower symmetry with a very shallow minimum for the respective torsional modes.
AB - MCSCF calculations are reported for the electronic ground state and the two lowest excited singlet states of cyclopentadiene. Molecular geometries have been optimized for each state individually and the complete harmonic force field calculated. Similar to the situation found for cis- and (trans-butadiene the CC double bond length significantly increases on electron excitation and the CC single bond length within the cis-butadiene substructure decreases. The changes in the vibrational frequencies and in the character of the vibrational modes on excitation is documented in detail. Whereas the electronic ground state and the 1 1B2 state have C2v symmetry (with the carbon ring system and the CH bonds in one plane) the 2 1A1 state is predicted to have a lower symmetry with a very shallow minimum for the respective torsional modes.
UR - http://www.scopus.com/inward/record.url?scp=0344758195&partnerID=8YFLogxK
U2 - 10.1016/0166-1280(94)80175-4
DO - 10.1016/0166-1280(94)80175-4
M3 - Article
AN - SCOPUS:0344758195
SN - 0166-1280
VL - 303
SP - 71
EP - 82
JO - Journal of Molecular Structure: THEOCHEM
JF - Journal of Molecular Structure: THEOCHEM
IS - C
ER -