Isotope effect of hydrogen and lithium hydride molecules. Application of the dynamic extended molecular orbital method and energy component analysis

Abstract

In order to explore the isotope effect including the nuclear–electronic coupling and nuclear quantum effects under the one-particle approximation, we apply the dynamic extended molecular orbital (DEMO) method and energy component analysis to the hydrogen and lithium hydride isotope molecules. Since the DEMO method determines both electronic and nuclear wave functions simultaneously by variationally optimizing all parameters embedded in the basis sets, the virial theorem is completely satisfied and guarantees the relation of the kinetic and potential energies. We confirm the isotope effect on internuclear distances, nuclear and electronic wave functions, dipole moment, the polarizability, and each energy component. In the case of isotopic species of the hydrogen molecule, the total energy decreases from the H2 to the T2 molecule due to the stabilization of the nuclear–electronic potential component, as well as the nuclear kinetic one. In the case of the lithium hydride molecule, the energy lowering by replacing 6Li with 7Li is calculated to be greater than that by replacing H with D. This is mainly caused by the small destabilization of electron–electron and nuclear–nuclear repulsion in 7LiH compared to 6LiH, while the change in the repulsive components from 6LiH to 6LiD increases.