Theoretical investigation of the halogen bonded complexes between carbonyl bases and molecular chlorine
© 2015 Wiley Periodicals, Inc.
| Publié dans: | Journal of computational chemistry. - 1984. - 36(2015), 11 vom: 30. Apr., Seite 821-32 |
|---|---|
| Auteur principal: | |
| Autres auteurs: | , , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2015
|
| Accès à la collection: | Journal of computational chemistry |
| Sujets: | Journal Article DFT MP2 carbonyl compounds halogen bond molecular chlorine |
| Résumé: | © 2015 Wiley Periodicals, Inc. 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 |
|---|---|
| Description: | Date Completed 15.05.2015 Date Revised 26.03.2015 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.23860 |