Journal of Chemical Physics, Vol.115, No.13, 5932-5942, 2001
Coupled cluster study of the (X)over-tilde(2)Pi and (A)over-tilde(2)Sigma(+) electronic states of the HCGe radical: Renner-Teller splitting and the effects of relativistic corrections
The (X) over tilde (2)Pi and (A) over tilde (2)Sigma (+) states of the germanium methylidyne radical (HCGe) have been investigated at the SCF, CISD, CCSD, and CCSD(T) levels of theory. The total energies, equilibrium geometries, dipole moments, harmonic vibrational frequencies, infrared intensities, and Renner-Teller splitting are reported. The relativistic one-electron Darwin and mass-velocity terms are calculated using first-order perturbation theory and the effects of these corrections on energetics, harmonic vibrational frequencies, and Renner-Teller splitting are discussed. At our highest level of theory [CCSD(T)/cc-pVQZ], the ground electronic state ((X) over tilde (2)Pi) has a linear geometry with r(e)(CH)=1.079 Angstrom and r(e)(CGe)=1.769 Angstrom, in good agreement with the experimental values of r(0)(CH)=1.067 Angstrom and r(0)(CGe)=1.776 Angstrom. In the electronically excited (A) over tilde (2)Sigma (+) state, HCGe is also found to have a linear geometry with r(e)(CH)=1.074 Angstrom and a much shorter r(e)(CGe)=1.669 Angstrom at the [CCSD(T)/cc-pVQZ] level, in agreement with experimental values of r(0)(CH)=1.059 Angstrom, r(0)(CGe)=1.674 Angstrom, and the observation of a C-Ge triple bond character. The (A) over tilde (2)Sigma (+) state C-Ge stretching vibrational frequency is determined to be omega (3)=990.2 cm(-1) at the CCSD(T)/cc-pVTZ level with the inclusion of relativistic effects, which is in essentially perfect agreement with the experimental value of nu (3)=990 cm(-1). With the same method, the (X) over tilde (2)Pi state harmonic vibrational frequencies are predicted to be 846 cm(-1) for the C-Ge stretching, 443 and 506 cm(-1) for the two nondegenerate bending Renner-Teller components, and 3249 cm(-1) for the C-H stretching modes for which experimental values are not available. The quantum mechanical splitting (T-0 value) was determined to be 38.0 kcal/mol at the nonrelativistic CCSD(T)/TZ3P(2 f,2d)+2diff level, while it is found to be 39.9 kcal/mol with the inclusion of relativity, in very good agreement with the experimental value of 39.8 kcal/mol. The Renner parameter (epsilon) is determined to be -0.1386, and the effects of relativity were seen to produce a smaller Renner parameter of -0.1329.