Issue 33, 2011

A theoretical study of pure and mixed caesium clusters and cluster ions, CslHmO 0/+n, l ≤ 5: geometry, energetics and photofragmentation

Abstract

Motivated by recent progress in the mass spectroscopy of the elementary reaction of alkali metals and water dispersed in ultracold helium nanodroplets (S. Müller et al., Phys. Rev. Lett., 2009, 102, 183401.), we investigate the properties of pure and mixed Cs clusters and cluster ions, CslHmO0/+n, from a quantum chemical perspective. The presence of Cs atoms requires a careful choice of the methodology, which we have tested for small molecules for which experimental results were available. With the thus selected density functional, pseudopotential and basis set, we compute the geometry, the ionization potentials and the atomization energy, enabling a proper estimate of the energetics of cluster fragmentation upon photoionization. Based upon these calculations, we are able to construct a fragmentation tree that rationalizes the origin of all peaks observed in the experimental mass spectrum. Infrared spectra are computed, and we introduce a simple mixed quantum-classical model that essentially reproduces the cluster geometries.

Graphical abstract: A theoretical study of pure and mixed caesium clusters and cluster ions, CslHmO0/+n, l ≤ 5: geometry, energetics and photofragmentation

Supplementary files

Article information

Article type
Paper
Submitted
21 Apr 2011
Accepted
20 Jun 2011
First published
14 Jul 2011

Phys. Chem. Chem. Phys., 2011,13, 14973-14983

A theoretical study of pure and mixed caesium clusters and cluster ions, CslHmO0/+n, l ≤ 5: geometry, energetics and photofragmentation

S. Krapf, M. Schill, S. Krötz and T. Koslowski, Phys. Chem. Chem. Phys., 2011, 13, 14973 DOI: 10.1039/C1CP21274E

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