TY - JOUR
T1 - Complete active space valence bond method applied to chemical reactions
AU - Nakano, Haruyuki
AU - Nakayama, Kenichi
AU - Hirao, Kimihiko
N1 - Funding Information:
The present research is supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture of Japan. The CASSCF and CASVB wave functions were obtained by a modified version of HONDO98 (Ref. [36] ). The perturbation calculations were carried out with an MR2D program (Refs. [37, 38] ). The orbital contour maps were plotted using a PLTORB program in GAMESS (Ref. [39] ).
PY - 1999/4/2
Y1 - 1999/4/2
N2 - A complete active space valence bond (CASVB) method with orthogonal and non-orthogonal orbitals is applied to the collinear exchange reaction H + H2 → H2 + H and the unimolecular dissociation H2CO → H2 + CO. The bond nature during the reactions is analyzed using the occupation number (weight) of the valence bond resonance structures. The CASVB descriptions with orthogonal and non-orthogonal orbitals give a similar picture, although the ratio of covalent vs. ionic bonds are quite different. In the H2CO → H2 + CO reaction, the CH bond dissociation and HH bond formation occur after passing through the transition state. CASVB gives a clear understanding of reaction mechanisms in terms of competing bonding schemes whose weights change along the intrinsic reaction coordinate.
AB - A complete active space valence bond (CASVB) method with orthogonal and non-orthogonal orbitals is applied to the collinear exchange reaction H + H2 → H2 + H and the unimolecular dissociation H2CO → H2 + CO. The bond nature during the reactions is analyzed using the occupation number (weight) of the valence bond resonance structures. The CASVB descriptions with orthogonal and non-orthogonal orbitals give a similar picture, although the ratio of covalent vs. ionic bonds are quite different. In the H2CO → H2 + CO reaction, the CH bond dissociation and HH bond formation occur after passing through the transition state. CASVB gives a clear understanding of reaction mechanisms in terms of competing bonding schemes whose weights change along the intrinsic reaction coordinate.
UR - https://www.scopus.com/pages/publications/0033515399
UR - https://www.scopus.com/pages/publications/0033515399#tab=citedBy
U2 - 10.1016/S0166-1280(98)00462-X
DO - 10.1016/S0166-1280(98)00462-X
M3 - Article
AN - SCOPUS:0033515399
SN - 0166-1280
VL - 461-462
SP - 55
EP - 69
JO - Journal of Molecular Structure: THEOCHEM
JF - Journal of Molecular Structure: THEOCHEM
ER -