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 170nm) 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 etal., 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.
Original language | English |
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Pages (from-to) | 4079-4089 |
Number of pages | 11 |
Journal | ChemPhysChem |
Volume | 17 |
Issue number | 24 |
Early online date | 27 Oct 2016 |
DOIs | |
Publication status | Published - 15 Dec 2016 |
Keywords
- Bond energy
- Density functional calculations
- Electronic structure
- Molecular modeling
- Surface chemistry
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
- Physical and Theoretical Chemistry