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The electronic spectra of 2‐(2′‐hydroxybenzoyl)pyrrole and 2‐(2′‐methoxybenzoyl)pyrrole: a theoretical study
Author(s) -
Ghigo Giovanni,
Ciofalo Maurizio,
Gagliardi Laura,
La Manna Gianfranco,
Cramer Christopher J.
Publication year - 2005
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.972
Subject(s) - chemistry , solvation , solvatochromism , pyrrole , spectral line , computational chemistry , hamiltonian (control theory) , cyclohexane , molecule , photochemistry , quantum mechanics , organic chemistry , physics , mathematical optimization , mathematics
The gas‐phase electronic spectra of 2‐(2′‐hydroxybenzoyl)pyrrole and 2‐(2′‐methoxybenzoyl)pyrrole have been determined using multiconfigurational perturbation theory (CASPT2). Solvatochromic spectral shifts for these molecules have been measured in cyclohexane and methanol and the electrostatic components of these shifts have been estimated using the vertical electrostatic model (VEM 4.2) developed for the configuration interaction with single excitations model implemented with the intermediate neglect of differential overlap Hamiltonian (CIS/INDO/S2). Comparison between theory and experiment and an interpretation of the main spectral differences between the two substituted pyrroles and their solvation are presented. Copyright © 2005 John Wiley & Sons, Ltd.