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

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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

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Publication details

The article was received on 29 Aug 2019, accepted on 30 Sep 2019 and first published on 08 Nov 2019


Article type: Paper
DOI: 10.1039/C9CP04790E
Phys. Chem. Chem. Phys., 2019, Advance Article
  • Open access: Creative Commons BY license
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    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, Advance Article , DOI: 10.1039/C9CP04790E

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