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Theoretical Investigation of the Halogen Bonded Complexes Between Carbonyl Bases and Molecular Chlorine

Tijdschriftbijdrage - Tijdschriftartikel

The halogen bonded complexes between six carbonyl bases and molecular chlorine are investigated theoretically. The interaction energies calculated at the CCSD(T)/aug-cc-pVTZ level range between -1.61 and -3.50 kcal mol(-1). These energies are related to the ionization potential, proton affinity, and also to the most negative values (V(s,min)) on the electrostatic potential surface of the carbonyl bases. A symmetry adapted perturbation theory decomposition of the energies has been performed. The interaction results in an elongation of the Cl-Cl bond and a contraction of the CF and CH bonds accompanied by a blue shift of the ν(CH) vibrations. The properties of the Cl2 molecules are discussed as a function of the σ*(Cl-Cl) occupation, the hybridization, and the occupation of the Rydberg orbitals of the two chlorine atoms. Our calculations predict a large enhancement of the infrared and Raman intensities of the ν(Cl-Cl) vibration on going from isolated to complexed Cl2.
Tijdschrift: Journal of Computational Chemistry
ISSN: 0192-8651
Issue: 11
Volume: 36
Pagina's: 821 - 832
Jaar van publicatie:2015
BOF-keylabel:ja
IOF-keylabel:ja
BOF-publication weight:1
CSS-citation score:1
Auteurs:International
Authors from:Higher Education