Premium
Monte Carlo–quantum mechanics study of the UV–visible spectrum of benzophenone in water
Author(s) -
Urahata Sergio,
Canuto Sylvio
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/1097-461x(2000)80:4/5<1062::aid-qua55>3.0.co;2-3
Subject(s) - solvatochromism , benzophenone , monte carlo method , quantum monte carlo , chemistry , blueshift , visible spectrum , molecular physics , physics , optics , photochemistry , molecule , photoluminescence , organic chemistry , statistics , mathematics
The ultraviolet–visible (UV–Vis) absorption spectrum of benzophenone is characterized by two broad bands associated to a weak n –π* and a strong π–π* transition. The theoretical description of the solvatochromic shift is an interesting challenge because in solvents the n –π* transition suffers a blue shift whereas the π–π* band suffers a red shift. This solvatochromism of benzophenone in water is studied theoretically in the entire UV–Vis region (up to 200 nm) using a combined Monte Carlo–quantum mechanics approach. The liquid structures are generated by NVT Metropolis Monte Carlo, and supermolecules are generated for subsequent quantum mechanical INDO/CIS calculations. Long simulations and stable ensemble averages are used. The results are in good qualitative agreement with experiment. The n –π* transition shifts toward the blue by +1170 cm −1 . The π–π* band is composed by several transitions. The most intense is calculated to shift toward the red by −1330 cm −1 . © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 1062–1067, 2000