Theoretical modeling of ionization energies of argon clusters: Nuclear delocalization effects

0360829 - ÚFCH JH 2012 RIV US eng J - Journal Article
Svrčková, P. - Vítek, A. - Karlický, F. - Paidarová, Ivana - Kalus, R.
Theoretical modeling of ionization energies of argon clusters: Nuclear delocalization effects.
Journal of Chemical Physics. Roč. 134, č. 22 (2011), s. 224310. ISSN 0021-9606. E-ISSN 1089-7690
Institutional research plan: CEZ:AV0Z40400503
Keywords : rare-gas clusters * electron-impact ionization * helium clusters
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.333, year: 2011

Temperature dependence of vertical ionization energies is modeled for small argon clusters (N <= 13) using classical parallel-tempering Monte Carlo methods and extended interaction models based on the diatomics-in-molecules approach. Quantum effects at the zero temperature are also discussed in terms of zero-point nuclear vibrations, either at the harmonic approximation level or at the fully anharmonic level using the diffusion Monte Carlo calculations. Both approaches lead to a considerable improvement of the theoretical predictions of argon clusters ionization energies and represent a realistic way of modeling of ionization energies for weakly bound and floppy complexes in general. A thorough comparison with a recent electron-impact experiment [O.Echt et al., J. Chem. Phys. 123, 084313 (2005)] is presented and a novel interpretation of the experimental data is proposed. (C) 2011 American Institute of Physics. [doi:10.1063/1.3599052]
Permanent Link: http://hdl.handle.net/11104/0198286