Molecular adsorption on solid surfaces and how the molecular vibrational properties are affected by the interaction with the surface is a widely studied phenomena not only for academic knowledge but also for potential applications. In the present work, to provide new theoretical insight we aim in overcoming the harmonic approximation by extending our divide-and-conquer semiclassical molecular dynamics approach [1] to the adsorption problem. Relying on a standard Born-Oppenheimer classical trajectory of the full dimensional surface-adsorbate system, we propagate at the semiclassical level the adsorbate modes and the more important coupled surface ones. In this way we are able to account with a contained computational effort not only for anharmonicities, but also for quantum nuclear effects, such as overtones and combination bands, even for these systems where there are a large number of degrees of freedom. TiO2 is one of the most promising metal oxide for photocatalitic applications, especially for the Anatase(101) facet. Consequently, we validated our approach for CO, NO and H2O adsorbed on the aforementioned surface, and compare our semiclassical results against the harmonic estimates and the classical power spectra, which are computed on top on the same trajectory that we used for the semiclassical simulations [2]. Since infrared spectra for H2O adsorbed on Anatase(101) are of difficult interpretation, we will give some new physical insight by applying our approach to this problem [3]. [1] M. Ceotto, et al., Phys. Rev. Lett. 119, 010401 (2017) [2] M. Cazzaniga, et al., J. Chem. Phys. 152, 104104 (2020) [3] M. Cazzaniga, et al., in preparation

Anharmonic calculations of vibrational spectra for molecular adsorbates : A divide-and-conquer semiclassical molecular dynamics approach / M. Cazzaniga, M. Micciarelli, F. Gabas, F. Finocchi, M. Ceotto. ((Intervento presentato al 4. convegno Molecular Simulations and Engineering-MolSimEng tenutosi a Milano nel 2021.

Anharmonic calculations of vibrational spectra for molecular adsorbates : A divide-and-conquer semiclassical molecular dynamics approach

M. Cazzaniga;M. Micciarelli;F. Gabas;M. Ceotto
2021

Abstract

Molecular adsorption on solid surfaces and how the molecular vibrational properties are affected by the interaction with the surface is a widely studied phenomena not only for academic knowledge but also for potential applications. In the present work, to provide new theoretical insight we aim in overcoming the harmonic approximation by extending our divide-and-conquer semiclassical molecular dynamics approach [1] to the adsorption problem. Relying on a standard Born-Oppenheimer classical trajectory of the full dimensional surface-adsorbate system, we propagate at the semiclassical level the adsorbate modes and the more important coupled surface ones. In this way we are able to account with a contained computational effort not only for anharmonicities, but also for quantum nuclear effects, such as overtones and combination bands, even for these systems where there are a large number of degrees of freedom. TiO2 is one of the most promising metal oxide for photocatalitic applications, especially for the Anatase(101) facet. Consequently, we validated our approach for CO, NO and H2O adsorbed on the aforementioned surface, and compare our semiclassical results against the harmonic estimates and the classical power spectra, which are computed on top on the same trajectory that we used for the semiclassical simulations [2]. Since infrared spectra for H2O adsorbed on Anatase(101) are of difficult interpretation, we will give some new physical insight by applying our approach to this problem [3]. [1] M. Ceotto, et al., Phys. Rev. Lett. 119, 010401 (2017) [2] M. Cazzaniga, et al., J. Chem. Phys. 152, 104104 (2020) [3] M. Cazzaniga, et al., in preparation
Settore CHIM/02 - Chimica Fisica
Politecnico di Milano
Anharmonic calculations of vibrational spectra for molecular adsorbates : A divide-and-conquer semiclassical molecular dynamics approach / M. Cazzaniga, M. Micciarelli, F. Gabas, F. Finocchi, M. Ceotto. ((Intervento presentato al 4. convegno Molecular Simulations and Engineering-MolSimEng tenutosi a Milano nel 2021.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/872399
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