American Institute of Physics, The Journal of Chemical Physics, 16(137), p. 164316
DOI: 10.1063/1.4762442
Full text: Unavailable
For high-precision calculations of rovibrational states of light molecules, it is essential to include non-adiabatic corrections. In the absence of crossings of potential energy surfaces, they can be incorporated in a single surface picture through coordinate-dependent vibrational and rotational reduced masses. We present a compact method for their evaluation and relate in particular the vibrational mass to a well defined nuclear core mass derived from a Mulliken analysis of the electronic density. For the rotational mass we propose a simple, but very effective parametrization. The use of these masses in the nuclear Schrödinger equation yields numerical data for the corrections of a much higher quality than can be obtained with optimized constant masses, typically better than 0.1 cm(-1). We demonstrate the method for H(2), H(2) (+), and singly deuterated isotopologues. Isotopic asymmetry does not present any particular difficulty. Generalization to polyatomic molecules is straightforward.