Accurate non-Born-Oppenheimer calculations of the complete pure vibrational spectrum of D-2 with including relativistic corrections

作者：Bubin Sergiy; Stanke Monika; Adamowicz Ludwik^*

来源：Journal of Chemical Physics, 2011, 135(7): 074110.

DOI：10.1063/1.3625955

• angular momentum
• deuterium
• fine structure
• relativistic corrections
• variational techniques
• vibrational states
• wave functions

In this work we report very accurate variational calculations of the complete pure vibrational spectrum of the D-2 molecule performed within the framework where the Born-Oppenheimer (BO) approximation is not assumed. After the elimination of the center-of-mass motion, D-2 becomes a three-particle problem in this framework. As the considered states correspond to the zero total angular momentum, their wave functions are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even non-negative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of alpha(2) (where alpha = 1/c is the fine structure constant) calculated as expectation values of the operators representing these effects.

• 出版日期2011-8-21