Darwin and mass-velocity relativistic corrections in non-Born-Oppenheimer variational calculations.
The Pauli approach to account for the mass-velocity and Darwin relativistic corrections has been applied to the formalism for quantum mechanical molecular calculations that does not assume the Born-Oppenheimer (BO) approximation regarding separability of the electronic and nuclear motions in molecular systems. The corrections are determined using the first order perturbation theory and are derived for the non-BO wave function of a diatomic system expressed in terms of explicitly correlated Gaussian functions with premultipliers in the form of even powers of the internuclear distance. As a numerical example we used calculations of the transition energies for pure vibrational states of the HD(+) ion.
Kedziera
Dariusz
D
Department of Chemistry, Nicholas Copernicus University, ul. Gagarina 7, PL 87-100 Toruń, Poland.
Stanke
Monika
M
Bubin
Sergiy
S
Barysz
Maria
M
Adamowicz
Ludwik
L