Multireference CI calculation of nuclear quadrupole coupling constants of CN+ and CN-: rovibrational dependence.
The 14N quadrupole coupling constants of rovibrational levels of the X1sigma+ and c1sigma+ states of CN+, and the ground electronic state of CN- are calculated from molecular wavefunctions which explicitly describe nuclear displacement. From the electronic states considered, the excited 1sigma+ state of CN is predicted to exhibit the strongest N coupling, at least in the ground vibrational state. Compared to the vibrational dependence of the 14N QCC's, which is found to be significant in all cases, the rotational dependence is predicted to be unimportant. Special attention is paid to the assessment of adequacy of the expectation value approach to the evaluation of the electric field gradient tensor within the applied multireference configuration interaction formalism. Spectroscopic constants are derived from corresponding potential energy curves to testify to the quality of the correlated wave functions used.
Polák
R
R
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague. rudolf.polak@jh-inst.cas.cz
Fiser
J
J
D003486:Cyanides / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D013057:Spectrum Analysis
D003486:Cyanides; D009584:Nitrogen