A Monte Carlo-quantum mechanics study of the solvatochromic shifts of the lowest transition of benzene

Autor:	Sylvio Canuto, Michael C. Zerner, Kaline Coutinho
Rok vydání:	2000
Předmět:	Cyclohexane Chemistry Monte Carlo method Solvatochromism General Physics and Astronomy Chromophore Supermolecule Molecular physics Solvent chemistry.chemical_compound Physical chemistry Molecule Physical and Theoretical Chemistry Benzene
Zdroj:	The Journal of Chemical Physics. 112:9874-9880
ISSN:	1089-7690 0021-9606
Popis:	We examine the spectroscopic red shifts that occur when benzene is dissolved in (liquid) benzene, in cyclohexane, in carbon tetrachloride, and in water. For this we develop a mixed classical/quantum model in which uncorrelated structures are obtained from Monte Carlo simulation, and these structures are then used for quantum chemical calculations including the chromophore and all solvent molecules within the first radial distribution maxima. We discuss the effects of different sampling techniques and the inclusion of more, or less, solvent molecules in the quantum chemical supermolecule calculation. We obtain shifts of −306 cm−1, −268 cm−1, −456 cm−1, and −122 cm−1, in excellent agreement with the experimentally observed shifts of −332 cm−1, −308 cm−1, −458 cm−1, and −143 cm−1, respectively. We note that the larger shift observed in carbon tetrachloride that is not expected on the basis of larger dielectric constant results from small contributions of the charge transfer type from solvent to solute.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::b8e5fe303c2b718c15ce83d4bbe0a29e https://doi.org/10.1063/1.481624 Zobrazit plný text záznamu