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Doctoral Thesis
DOI
10.11606/T.43.1997.tde-22062012-154558
Document
Author
Full name
Kaline Rabelo Coutinho
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 1997
Supervisor
Committee
Oliveira, Mario Jose de (President)
Antonelli, Alex
Carneiro, Carlos Eugenio Imbassahy
Freitas, Luiz Carlos Gomide
Nascimento, Marco Antonio Chaer
Title in Portuguese
Modelo discreto de solvente. Solvatocromismo no espectro de absorção molecular
Keywords in Portuguese
Efeitos de Solvente
Espectro de Absorção Molecular
Método Monte Carlo
Simulação computacional de líquidos
Solvatocromismo
Abstract in Portuguese
Um procedimento baseado no uso sequencial de simulação Monte Carlo e cálculos de Mecânica Quântica é proposto e usado para o tratamento de efeitos de solvente, com especial atenção parao sovatocromismo no espectro de absorção molecular. A ideia básica é realizar simulações clássicas com o método Monte Carlo para gerar estruturas supermoleculares do sistema em solução e em seguida tratar estas supermoléculas (soluto, solvente e suas interações) com cálculos quânticos. Um modelo totalmente discreto do solvente é utilizado e, portanto, o uso de meios dielétricos contínuos é dispensado. Neste procedimento, as supermoléculas são compostas por uma molécula do soluto rodeada pela primeira camada de solvatação definida através da função distribuição. Os efeitos de solvente são calculados usando médias configuracionais sobre estruturas supermoleculares descorrelacionadas obtidas através de análises estatísticas das simulações. Como aplicação, os deslocamentos espectrais da primeira banda de absorção do benzeno 1B2u(- *), devido a presença de diversos solventes, foram analisados e calculados. Boa concordância com os resultados experimentais foram obtidos.
Title in English
Discrete model of the solvent. Solvatochromic at the absorption spectrum molecular.
Keywords in English
Computer simulation of liquids
Molecular Absorption Spectrum
Monte Carlo method
solvatochromism
solvent effects
Abstract in English
A approach based on the sequential use of Monte Carlo simulation and Quantum Mechanics is proposed and use for the treatment of solvent effects with special attention to solvatochromic shifts. The basic Idea is to perform a classical Monte Carlo simulation to generate supermolecular structures of the system, then to treat these supermolecules (solute, solvent and all its interaction) by quantum mechanics. This is a totally discrete modelo f the solvent that avoids the use of a dielectric continuum. In this approach, the supermolecules are composed by the solute molecule surrounded by the first solvation Shell as determined by the distribution function. The solvent effects are calculated using ensemble average over uncorrelated supermolecular structures obtained by statistical analysis. As na application, the spectral shifts of the 1B2u(- *) trnsition of benzene in different solvents are investigated. Good agreement with the experimental results are obtained.
 
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45405Coutinho.pdf (67.61 Mbytes)
Publishing Date
2012-06-22
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • CANUTO, Sylvio, COUTINHO, Kaline, and ZERNER, M. C. Including Dispersion in Configuration Interaction-Singles Calculations for the Spectroscopy of Chromophores in Solution [doi:10.1063/1.481332]. Journal of Chemical Physics [online], 2000, vol. 112, n. 17, p. 7293-7299.
  • COUTINHO, Kaline, and CANUTO, Sylvio. Solvent Effects from a Sequential Monte Carlo - Quantum Mechanical Approach [doi:10.1016/S0065-3276(08)60209-9]. Advances in Quantum Chemistry [online], 1997, vol. 28, p. 89-105.
  • COUTINHO, Kaline, CANUTO, Sylvio, and ZERNER, M. C. A Monte Carlo-Quantum Mechanics Study of the Solvatochromic Shifts of the Lowest Transition of Benze [doi:10.1063/1.481624]. Journal of Chemical Physics [online], 2000, vol. 112, n. 22, p. 9874-9880.
  • COUTINHO, Kaline, CANUTO, Sylvio, and ZERNER, M.C. Calculation of the Absorption Spectrum of Benzene in Condensed Phase : A Study of the Solvent Effects [doi:10.1002/(SICI)1097-461X(1997)65:5<885::AID-QUA52>3.0.CO;2-V]. International Journal of Quantum Chemistry [online], 1997, vol. 65, n. 5, p. 885-891.
  • COUTINHO, Kaline, e CANUTO, Sylvio. Estudo Teórico de Espectroscopia de Absorção de Líquidos Moleculares. Química Nova [online], 1994, vol. 17, n. 6, p. 480-482. [acesso 2016-08-14]. Disponível em : <http://submission.quimicanova.sbq.org.br/qn/qnol/1994/vol17n6/v17_n6_%20%285%29.pdf>
  • COUTINHO, Kaline, OLIVEIRA, M. J., and CANUTO, Sylvio. Sampling Configurations in Monte Carlo Simulations for Quantum Mechanical Studies of Solvent Effects [doi:10.1002/(SICI)1097-461X(1998)66:3<249::AID-QUA6>3.0.CO;2-V]. International Journal of Quantum Chemistry [online], 1998, vol. 66, n. 3, p. 249-253.
  • URAHATA, Sérgio, COUTINHO, Kaline, and CANUTO, Sylvio. Hydrophobic Interaction and Solvatochromic Shift of Benzene in Water [doi:10.1016/S0009-2614(97)00642-8]. Chemical Physics Letters [online], 1997, vol. 274, n. 1-3, p. 269-274.
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