Theoretical study of the UV-induced desorption of molecular oxygen from the reduced TiO2 (110) surface

Autor:	M. P. de Lara-Castells, Jeffrey L. Krause
Rok vydání:	2003
Předmět:	Photoexcitation Condensed Matter::Materials Science Dipole Vibronic coupling Atomic orbital Chemistry Desorption Cluster (physics) General Physics and Astronomy Physical and Theoretical Chemistry Atomic physics Ground state Excitation
Zdroj:	The Journal of Chemical Physics. 118:5098-5105
ISSN:	1089-7690 0021-9606
DOI:	10.1063/1.1545093
Popis:	We investigate the UV-induced desorption of O2 from a reduced TiO2 rutile surface. The desorption mechanism considered is a direct, optical excitation of the adsorbate-substrate complex. The low-lying excited electronic states of the adsorbate-surface system and the transition dipole moments are calculated with a cluster model. We also estimate the effects of nonadiabatic coupling on the desorption yield. As a consequence of the localized nature of the adsorption process, ground state properties calculated with the cluster model agree well with previous results obtained with a slab model. To reduce the size of the calculation, we use optimal orbitals for each of the interacting electronic states, followed by transformation to biorthonormal orbital sets. Comparison with experimental photodesorption cross-section data shows excellent agreement for photon energies close to the vertical transition energy. At higher energies, we speculate that substrate-mediated electronic excitation mechanisms must be include...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::ba521f01c4d88cec93e874125f553ca3 https://doi.org/10.1063/1.1545093 Zobrazit plný text záznamu