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Determining the Intermolecular Structure in the S 0 and S 1 States of the Phenol Dimer by Rotationally Resolved Electronic Spectroscopy
Author(s) -
Schmitt Michael,
Böhm Marcel,
Ratzer Christian,
Krügler Daniel,
Kleinermanns Karl,
Kalkman Ivo,
Berden Giel,
Meerts W. Leo
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500670
Subject(s) - intermolecular force , chemistry , ab initio quantum chemistry methods , dimer , ab initio , excited state , hydrogen bond , electronic structure , molecular physics , bond length , spectroscopy , computational chemistry , atomic physics , crystallography , molecule , crystal structure , physics , organic chemistry , quantum mechanics
The rotationally resolved UV spectra of the electronic origins of five isotopomers of the phenol dimer have been measured. The complex spectra are analyzed using a fitting strategy based on a genetic algorithm. The intermolecular geometry parameters have been determined from the inertial parameters for both electronic states and compared to the results of ab initio calculations. In the electronic ground state, a larger hydrogen‐bond length than in the ab initio calculations is found together with a smaller tilt angle of the aromatic rings, which shows a more pronounced dispersion interaction. In the electronically excited state, the hydrogen‐bond length decreases, as has been found for other hydrogen‐bonded clusters of phenol, and the two aromatic rings are tilted less toward each other.