The vibrational g-factor of dihydrogen from theoretical calculation and analysis of vibration-rotational spectra

Phys Chem Chem Phys. 2005 Apr 21;7(8):1747-58. doi: 10.1039/b500992h.

Abstract

We present the first results from quantum-chemical calculation of a vibrational g-factor; the calculations were performed at the level of full configuration interaction using a basis set of aug-cc-pVQZ quality. The theoretical results are consistent with experimental results from analysis of pure rotational and vibration-rotational spectra of dihydrogen in six isotopic variants, in which calculated results for either the rotational g-factor or adiabatic corrections are employed to constrain fits of coefficients of radial functions from wave numbers of transitions. When fits are constrained with data for the rotational g-factor, we reproduce also the radial dependence of adiabatic corrections relative to their value at equilibrium internuclear separation.

MeSH terms

  • Algorithms
  • Hydrogen / chemistry*
  • Quantum Theory
  • Rotation
  • Vibration

Substances

  • Hydrogen