Computational Study of the Interactions between Benzene and Crystalline Ice I<sub>h</sub>: Ground and Excited States

Sharma, Divya; Sameera, W. M. C.; Andersson, Stefan; Nyman, Gunnar; Paterson, Martin J.

doi:10.1002/cphc.201600660

Cited by 5 publications

(5 citation statements)

References 104 publications

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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%

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Dawes

Pascual

Mason

et al. 2018

Phys. Chem. Chem. Phys.

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We present results of a combined vacuum ultraviolet (VUV) and infrared (IR) photoabsorption study of amorphous benzene : water mixtures and layers to investigate the benzene-water interaction in the solid phase. VUV spectra of 1 : 1, 1 : 10 and 1 : 100 benzene : water mixtures at 24 K reveal a concentration dependent shift in the energies of the 1B2u, 1B1u and 1E1u electronic states of benzene. All the electronic bands blueshift from pure amorphous benzene towards gas phase energies with increasing water concentration. IR results reveal a strong dOH-π benzene-water interaction via the dangling OH stretch of water with the delocalised π system of the benzene molecule. Although this interaction influences the electronic states of benzene with the benzene-water interaction causing a redshift in the electronic states from that of the free benzene molecule, the benzene-benzene interaction has a more significant effect on the electronic states of benzene. VUV spectra of benzene and water layers show evidence of non-wetting between benzene and water, characterised by Rayleigh scattering tails at wavelengths greater than 220 nm. Our results also show evidence of benzene-water interaction at the benzene-water interface affecting both the benzene and the water electronic states. Annealing the mixtures and layers of benzene and water show that benzene remains trapped in/under water ice until water desorption near 160 K. These first systematic studies of binary amorphous mixtures in the VUV, supported with complementary IR studies, provide a deeper insight into the influence of intermolecular interactions on intramolecular electronic states with significant implications for our understanding of photochemical processes in more realistic astrochemical environments.

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Section: Benzene and Water Mixturessupporting

confidence: 93%

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Dawes

Pascual

Mason

et al. 2018

Phys. Chem. Chem. Phys.

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“…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%

Electronic excited states of benzene in interaction with water clusters: influence of structure and size

2021

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This work is dedicated to the theoretical investigation of the influence of water clusters' organisation and size on the electronic spectrum of an interacting benzene (Bz) molecule using both TD-DFT and CASPT2 approaches. The geometries were extracted from two benzene-hexagonal ice configurations leading to maximum/minimum ionization energies (Geo IEI /Geo IED series) [1]. An appropriate basis set containing atomic diffuse and polarisation orbitals and describing the Rydberg states of Bz was determined. The TD-DFT approach was carefully benchmarked against CASPT2 results for the smallest systems. Despite some discrepancies, the trends were found to be similar at both levels of theory: the positions and intensities of the main π → π transitions were found slightly split due to symmetry breaking. For the smallest systems, our results clearly show the dependence of the electronic transitions on the clusters' structures. Of particular interest, a π →Rydberg orbital transition of non negligible oscillator strength, the Rydberg orbital being expanded on the water cluster, was found for the Geo IED series only. It was found lower than 7 eV ie more than 2 eV below the ionization potential of Bz. When the cluster' size increases, similar transitions are found for all structures, the Rydberg orbitals becoming mainly developed on the H atoms of the water molecules at the edge of the cluster. Given their nature and energy, such

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“…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%

ONIOM(QM:AMOEBA09) Study on Binding Energies and Binding Preference of OH, HCO, and CH₃ Radicals on Hexagonal Water Ice (I_h)

et al. 2017

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We have combined the AMOEBA09 polarizable force field with the ONIOM(QM:MM) method to rationalize binding energies and binding preferences of the OH, HCO, and CH 3 radicals on crystalline water ice (I h ). O N I O M ( M 0 6 2 X : A M O E B A 0 9 ) a n d O N I O M -(wB97XD:AMOEBA) calculations suggest that the dangling hydrogen (d-H) or dangling oxygen (d-O) on the binding sites play an important role on the binding energies. Depending on the dangling nature at the binding site, a range of binding energies is found for the OH radical (0.67−0.20 eV), HCO radical (0.42−0.12 eV), and CH 3 radical (0.26−0.11 eV). The binding energies of these radicals are larger in the presence of both d-H and d-O at the binding site. On the other hand, binding energies are weaker in the presence of only d-H or d-O at the binding site. The ONIOM(QM:AMOEBA09) methodology is found to be a useful approach to calculate binding energies of atoms, radicals, and molecules on I h .

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Computational Study of the Interactions between Benzene and Crystalline Ice I_h: Ground and Excited States

Cited by 5 publications

References 104 publications

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Electronic excited states of benzene in interaction with water clusters: influence of structure and size

ONIOM(QM:AMOEBA09) Study on Binding Energies and Binding Preference of OH, HCO, and CH₃ Radicals on Hexagonal Water Ice (I_h)

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Computational Study of the Interactions between Benzene and Crystalline Ice Ih: Ground and Excited States

Cited by 5 publications

References 104 publications

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy

Electronic excited states of benzene in interaction with water clusters: influence of structure and size

ONIOM(QM:AMOEBA09) Study on Binding Energies and Binding Preference of OH, HCO, and CH3 Radicals on Hexagonal Water Ice (Ih)

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Computational Study of the Interactions between Benzene and Crystalline Ice I_h: Ground and Excited States

ONIOM(QM:AMOEBA09) Study on Binding Energies and Binding Preference of OH, HCO, and CH₃ Radicals on Hexagonal Water Ice (I_h)