Considerable matrix shift in the electronic transitions of helium-solvated cesium dimer cation Cs₂He.

ABSTRACT: We investigate the photodissociation of helium-solvated cesium dimer cations using action spectroscopy and quantum chemical calculations. The spectrum of Cs₂He⁺ shows three distinct absorption bands into both bound and dissociative states. Upon solvation with further helium atoms, considerable shifts of the absorption bands are observed, exceeding 0.1 eV (850 cm^-1) already for Cs₂He₁₀⁺, along with significant broadening. The shifts are highly sensitive to the character of the excited state. Our calculations show that helium atoms adsorb on the ends of Cs₂⁺. The shifts are particularly pronounced if the excited state orbitals extend to the area occupied by the helium atoms. In this case, Pauli repulsion

SUBMITTER: Kranabetter L 

PROVIDER: S-EPMC7116336 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature