CASSCF and CCI study of the photochemistry of HCo(CO)/sub 4/

Journal Article · Wed Jun 08 00:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00220a012· OSTI ID:7200558

Veillard, A; Strich, A

The photochemistry of HCo(CO)/sub 4/ has been studied theoretically through ab initio contracted configuration interaction (CCI) calculations of the potential energy curves which connect the ground and low excited states of HCo(CO)/sub 4/ with the ground and excited states of the products: HCo(CO)/sub 4/ hv/ ..-->.. H/sup ./ + /sup ./Co(CO)/sub 4/ HCo(CO)/sub 4/ hv/ ..-->.. CO + HCo(CO)/sub 3/. The calculations were carried out for the dissociation of the axial ligands (hydrogen or carbonyl) under C/sub 3v/ constraint, with a basis set which as at least of double-zeta quality. The CCI calculations, which correlate the metal 3d electrons and the two electrons of the Co-H bond, are based on a CASSCF reference wave function with six electrons in six active orbitals (3d/sub delta/, 4d/sub delta/, sigma/sub Co-H/, and sigma*/sub Co-H/), optimized for the /sup 3/A/sub 1/ sigma ..-->.. sigma* state. It is proposed that the photochemistry of HCo(CO)/sub 4/ occurs through excitation to the /sup 1/E d/sub delta/ ..-->.. sigma* state followed by intersystem crossing to the /sup 3/A/sub 1/ state.

• Research Organization: CNRS, Strasbourg (France)
• OSTI ID: 7200558
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:12; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CARBONYLS
CHEMISTRY
COBALT COMPOUNDS
CONFIGURATION INTERACTION
DATA
ENERGY LEVELS
EXCITED STATES
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
THEORETICAL DATA
TRANSITION ELEMENT COMPOUNDS