Issue 45, 2019

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

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 leads to a deformation of the excited state orbitals, resulting in the observed blue shift of the transition. Since the position of the weakly bound helium atoms is ill defined, Pauli repulsion also explains the broadening.

Graphical abstract: Considerable matrix shift in the electronic transitions of helium-solvated cesium dimer cation Cs2He+n

Supplementary files

Article information

Article type
Paper
Submitted
29 aug 2019
Accepted
30 sep 2019
First published
08 nov 2019
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2019,21, 25362-25368

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

L. Kranabetter, N. K. Bersenkowitsch, P. Martini, M. Gatchell, M. Kuhn, F. Laimer, A. Schiller, M. K. Beyer, M. Ončák and P. Scheier, Phys. Chem. Chem. Phys., 2019, 21, 25362 DOI: 10.1039/C9CP04790E

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