Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN

Journal Article · Tue Feb 22 04:00:00 EST 2000 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.480516· OSTI ID:20215432

Boldyrev, Alexander I ^[1]; Li, Xi ^[2]; Wang, Lai-Sheng ^[2]

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1. Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300 (United States)
2. Department of Physics, Washington State University, Richland, Washington 99352 (United States)

Vibrationally resolved photoelectron spectroscopy is combined with ab initio calculations to investigate the structure and chemical bonding in CuCN, CuCN{sup -}, AgCN, and AgCN{sup -}. The photoelectron spectra were measured at two photon energies, 532 and 355 nm and only detachment to the ground state of the neutral was observed at both detachment energies. The adiabatic electron affinity and metal-C vibrational frequency were obtained to be 1.466 (0.010) eV and 480(30) cm-1, 1.588 (0.010) eV and 390(30) cm-1 for CuCN and AgCN, respectively. In the ab initio calculations, both CuCN and CuCN{sup -} were found to have linear C{sub {infinity}}{sub V} structures. Isocyanide CuNC and CuNC{sup -} were found to be 10.7 and 6.5 kcal/mol [at the CCSD(T)/6-311+G(3d)//CCSD(T)/6-311+G{sup *} level of theory] higher in energy. Cyclic structures were found to be transition states for the cyanide-isocyanide isomerization. The calculated electron binding energies and vibrational frequency are in good agreement with the experimental measurements. The combined experimental and theoretical efforts allow us to elucidate the structures of CuCN and CuCN{sup -}, and the nature of their chemical bonding. (c) 2000 American Institute of Physics.

• OSTI ID: 20215432
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 112; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
AFFINITY
ANIONS
BINDING ENERGY
CHEMICAL BONDS
COPPER COMPOUNDS
CYANIDES
EXPERIMENTAL DATA
ISOMERIZATION
MOLECULAR STRUCTURE
PHOTOELECTRON SPECTROSCOPY
SILVER COMPOUNDS
THEORETICAL DATA
VIBRATIONAL STATES