title: Computational Study of the Interactions between Benzene and Crystalline Ice Ih: Ground and Excited States.
abstract: Ground-state geometries of benzene on crystalline ice cluster model surfaces (Ih) are investigated. It is found that the binding energies of benzene-bound ice complexes are sensitive to the dangling features of the binding sites. We used time-dependent DFT to study the UV spectroscopy of benzene, ice clusters, and benzene-ice complexes, by employing the M06-2X functional. It is observed that the size of the ice cluster and the dangling features have minor effects on the UV spectral characteristics. Benzene-mediated electronic excitations of water towards longer wavelengths (above 170 nm) are noted in benzene-bound ice clusters, where the cross-section of photon absorption by water is negligible, in good agreement with recent experimental results (Thrower et al., J. Vac. Sci. Technol. A, 2008, 26, 919-924). The intensities of peaks associated with water excitations in benzene-ice complexes are found to be higher than in isolated ice clusters. The π→π* electronic transition of benzene in benzene-ice complexes undergoes a small redshift compared with the isolated benzene molecule, and this holds for all benzene-bound ice complexes.
authors.affiliation: Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh, EH14 4AS, United Kingdom.
authors.forename: Divya
authors.initials: D
authors.lastname: Sharma
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, 606-8103, Japan.|University of Gothenburg, Department of Chemistry and Molecular Biology, Kemigården 4, 412 96, Gothenburg, Sweden.
authors.forename: W M C
authors.initials: WM
authors.lastname: Sameera
authors.affiliation: University of Gothenburg, Department of Chemistry and Molecular Biology, Kemigården 4, 412 96, Gothenburg, Sweden.|SINTEF Materials and Chemistry, P.O. Box 4760, 7465, Trondheim, Norway.
authors.forename: Stefan
authors.initials: S
authors.lastname: Andersson
authors.affiliation: University of Gothenburg, Department of Chemistry and Molecular Biology, Kemigården 4, 412 96, Gothenburg, Sweden.
authors.forename: Gunnar
authors.identifier: http://orcid.org/0000-0002-9527-3890
authors.initials: G
authors.lastname: Nyman
authors.affiliation: Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot Watt University, Edinburgh, EH14 4AS, United Kingdom.
authors.forename: Martin J
authors.identifier: http://orcid.org/0000-0002-0012-974X
authors.initials: MJ
authors.lastname: Paterson
keywords: bond energy; density functional calculations; electronic structure; molecular modeling; surface chemistry