Computational Study of the Interactions between Benzene and Crystalline Ice Ih: Ground and Excited States. Issue 24 (27th October 2016)

• Record Type: Journal Article
• Authors: Sharma, Divya; Sameera, W. M. C.; Andersson, Stefan; Nyman, Gunnar; Paterson, Martin J.
• Is Part Of: Chemphyschem. Volume 17:Issue 24(2016)
• Page Start: 4079
• Page End: 4089
• Publication Date: 2016-10-27
• Subjects: bond energy -- density functional calculations -- electronic structure -- molecular modeling -- surface chemistry; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201600660
• Languages: English
• ISSNs: 1439-4235

Abstract

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. Abstract : Benzene on ice : Benzene‐mediated electronic excitations of water towards longer wavelengths (above 170 nm) are noted in benzene‐bound ice clusters, which are however completely absent in isolated water ice clusters because the photon absorption cross‐section of water is negligible at these wavelengths.