In this work we report very accurate variational calculations of the two lowest vibrational states of the D2 and T2 molecules within the framework that does not assume the Born-Oppenheimer approximation. The non-relativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α2 calculated as expectation values of the operators representing these effects. The ν=0→1 transition energy of D2 obtained in the calculations is compared with the transition frequency obtained from the experimental spectra. The comparison shows the need to include corrections higher than second-order in α to further improve the agreement between the theory and the experiment.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Physics and Astronomy(all)