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Geometry of an Isolated Dimer of Imidazole Characterised by Rotational Spectroscopy and Ab Initio Calculations
Author(s) -
Mullaney John C.,
Zaleski Daniel P.,
Tew David P.,
Walker Nicholas R.,
Legon Anthony C.
Publication year - 2016
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.201501179
Subject(s) - dimer , imidazole , chemistry , ab initio , ab initio quantum chemistry methods , rotational spectroscopy , conformational isomerism , spectroscopy , intermolecular force , monomer , energy minimization , crystallography , molecular physics , computational chemistry , geometry , molecule , stereochemistry , organic chemistry , physics , quantum mechanics , polymer , mathematics
An isolated, gas‐phase dimer of imidazole is generated through laser vaporisation of a solid rod containing a 1:1 mixture of imidazole and copper in the presence of an argon buffer gas undergoing supersonic expansion. The complex is characterised through broadband rotational spectroscopy and is shown to have a twisted, hydrogen‐bonded geometry. Calculations at the CCSD(T)(F12*)/cc‐pVDZ‐F12 level of theory confirm this to be the lowest‐energy conformer of the imidazole dimer. The distance between the respective centres of mass of the imidazole monomer subunits is determined to be 5.2751(1) Å, and the twist angle γ describing rotation of one monomer with respect to the other about a line connecting the centres of mass of the monomers is determined to be 87.9(4)°. Four out of six intermolecular parameters in the model geometry are precisely determined from the experimental rotational constants and are consistent with results calculated ab initio.