2016
DOI: 10.1002/cphc.201600660
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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 (I ) 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-med… Show more

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Cited by 5 publications
(5 citation statements)
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References 104 publications
(218 reference statements)
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“…So the benzene-water interaction in fact lowers the excitation energies of benzene by 0.01 eV, 0.11 eV and 0.18 eV for the 1 B 2u , 1 B 1u and 1 E 1u states respectively. Indeed TD-DFT calculations of VUV spectra of benzene-ice clusters by Sharma et al 27 show small redshifts (0.05-0.12 eV) in the bands due to the 1 B 2u ' 1 A 1g and 1 B 1u ' 1 A 1g compared with isolated benzene in agreement with our results. The authors also describe a redshift in the 1 E 1u ' 1 A 1g band of between 0.04 and 0.12 eV depending on the nature of the binding site of the ice surface.…”
Section: Benzene and Water Mixturessupporting
confidence: 93%
“…So the benzene-water interaction in fact lowers the excitation energies of benzene by 0.01 eV, 0.11 eV and 0.18 eV for the 1 B 2u , 1 B 1u and 1 E 1u states respectively. Indeed TD-DFT calculations of VUV spectra of benzene-ice clusters by Sharma et al 27 show small redshifts (0.05-0.12 eV) in the bands due to the 1 B 2u ' 1 A 1g and 1 B 1u ' 1 A 1g compared with isolated benzene in agreement with our results. The authors also describe a redshift in the 1 E 1u ' 1 A 1g band of between 0.04 and 0.12 eV depending on the nature of the binding site of the ice surface.…”
Section: Benzene and Water Mixturessupporting
confidence: 93%
“…These intense excitations are not pure π → π as the latter are combined with π → Ry and n O → Ry transitions. Interestingly, regarding these transitions, our results differ from those obtained by Sharma et al [28] who computed a redshift of these bands with respect to those within isolated Bz when increasing the size of the water clusters, up to describing the Ih water ice environment using a QM/MM appproach. However, as previously mentioned in the introduction, they used a different functional from ours (M062X, that is not a long range corrected functional) and a basis set that does not describe the Rydberg states of Bz.…”
Section: Geo Iei−1 and Geo Ied−1contrasting
confidence: 99%
“…They used the 6-31++G(d,p) basis set that is not expected to describe properly the Rydberg states of benzene but the authors do not focus on the correct description of the latter states. Sharma et al [28] pursued their study expanding the benzene environnment. They computed TD-DFT spectra of Bz adsorbed on Ih water ice using the ONIOM(QM:MM) formalism with the QM part at the MO62X/6-31++G(d,p) level and the MM part using AMOEBA09.…”
Section: Introductionmentioning
confidence: 99%
“…The M062X and wB97XD density functionals have been shown to perform well for binding energies of water clusters and surfaces. 58,59 Therefore, we have used these two density functionals for the QM part. The 6-31+G(d,p) basis sets were used for the atoms in the QM region.…”
Section: ■ Computational Methodsmentioning
confidence: 99%
“…In our study, QM/MM cluster model structures of the binding sites were fully optimized with two methods: ONIOM­(M062X:AMOEBA09) and ONIOM­(wB97XD:AMOEBA09). The M062X and wB97XD density functionals have been shown to perform well for binding energies of water clusters and surfaces. , Therefore, we have used these two density functionals for the QM part. The 6-31+G­(d,p) basis sets were used for the atoms in the QM region. The counterpoise approach was used to determine the basis set superposition error (BSSE). , …”
Section: Computational Methodsmentioning
confidence: 99%