CONFIGURATION-INTERACTION SPECTROSCOPIC PROPERTIES OF X-2-SIGMA+ HNC+ AND X-2-PI HCN+

被引:20
作者
PETERSON, KA
MAYRHOFER, RC
WOODS, RC
机构
[1] Department of Chemistry, University of Wisconsin-Madison, Madison
关键词
D O I
10.1063/1.458683
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Stretching potential energy and dipole moment functions have been calculated for the ground electronic states of the HNC+ (X 2Σ+) and HCN+ (X 2Π) radical ions by singles and doubles configuration interaction (CI-SD) with a basis set of 74 contracted Gaussian-type orbitals. By comparison to analogous calculations on the CN radical, the ground state rotational constants B 0 of HNC+ and HCN+ are predicted to be 47, 122 ± 70 MHz and 40, 185 ± 70 MHz, respectively, by CI-SD with the addition of a size consistency correction, designated CI-SD(s). Stretching band origins and intensities have been obtained from the analytical potential energy and dipole moment functions using variational methods. The stretching fundamental band origins, v1 and V3, and their intensities are predicted to be 3464 cm-1/2507 cm-2 atm-1 and 2212 cm-1/2.3 cm-2 atm-1, respectively, for HNC+ and 3099 cm-1/1189 cm-2 atm-1 and 1806 cm-1/70.3 cm-2 atm-1 for HCN +. The equilibrium dipole moment of HNC+ calculated by CI-SD is just 0.66 D, while that of HCN+ is 3.63 D. In agreement with earlier studies the HNC+ isomer is predicted to be lower in energy than HCN+, and our calculated energy of isomerization, 18.91 kcal/mol, is in good agreement with this previous work. The Renner-Teller effect in the HCN+ isomer is predicted within the harmonic approximation by CI-SD(s) to be small, with the Renner parameter e and the Renner-Teller constant εω2 being - 0.056 and - 39.2 cm-1, respectively (ω2 = 696 cm-1). Quadrupole coupling constants have also been computed for HNC+ and HCN+, as well as for the neutrals HCN and HNC. The proton affinity at zero temperature PA0 of CN is 150.6 kcal/mol by CI-SD(s), and the adiabatic ionization potentials of HNC and HCN are 273.3 and 307.7 kcal/mol. © 1990 American Institute of Physics.
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页码:4946 / 4953
页数:8
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