Low-energy excitations in helium-like dimer within an exact diagonalization approach

Abstract

The non-relativistic quantum-mechanical problem on bound states of four interacting spinless electrons moving in the Coulomb field of two attractive point centers with Z0=2 spaced at fixed distance R0 (4He2 dimer within Born–Oppenheimer–Heitler–London approximation) has been solved rigorously through exact diagonalization (expansion on truncated orthonormalized basis) method. The four-spin-conditioned relativistic corrections (of order ∼1/c2) to the ground state level of the dimer have been calculated with exact diagonalization on spin cluster, the spectrum and eigenvectors of the spin problem have been obtained. It is shown that pair spin coupling is antiferromagnetic with exchange constant of 12 K (it provides antisymmetry of the spin-singlet ground-state wave function for isolated 4He atom with two fermions coupled within the unitary spatially symmetric shell), but within four-electron shell of 4He2 dimer this fact yields the quintet ground state of the four-spin cluster totally antisymmetric relative to pair permutations. The exchange within the interatomic bond depends on the interatomic distance, so that there is a coupling between spin and phonon degrees of freedom which leads to renormalization of phonon spectrum in condensed phase as compared to the corresponding spinless medium. This effect can be interpreted as a direct analog of translation-rotation interaction in molecular cryocrystals.