Photochemistry of Hydrogen Halides on Water Clusters: Simulations of Electronic Spectra and Photodynamics, and Comparison with Photodissociation Experiments

0360626 - ÚFCH JH 2012 RIV US eng J - Journal Article
Ončák, Milan - Slavíček, P. - Fárník, Michal - Buck, U.
Photochemistry of Hydrogen Halides on Water Clusters: Simulations of Electronic Spectra and Photodynamics, and Comparison with Photodissociation Experiments.
Journal of Physical Chemistry A. Roč. 115, č. 23 (2011), s. 6155-6168. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA AV ČR KAN400400651; GA ČR GA203/09/0422
Institutional research plan: CEZ:AV0Z40400503
Keywords : photochemistry * photodynamics * electronic spectra
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.946, year: 2011

The photochemistry of small HX·(H2O)n, n = 4 and 5 and X = F, Cl, and Br, clusters has been modeled by means of ab initio-based molecular simulations. The theoretical results were utilized to support our interpretation of photodissociation experiments with hydrogen halides on ice nanoparticles HX·(H2O)n, n ≈ 102−103. We have investigated the HX·(H2O)n photochemistry for three structural types: covalently bound structures (CBS) and acidically dissociated structures in a form of contact ion pair (CIP) and solvent separated pair (SSP). For all structures, we have modeled the electronic absorption spectra using the reflection principle combined with a path integral molecular dynamics (PIMD) estimate of the ground state density. In addition, we have investigated the solvent effect of water on the absorption spectra within the nonequilibrium polarizable continuum model (PCM) scheme.
Permanent Link: http://hdl.handle.net/11104/0006492