Title Direct measurement of the stability of the supramolecular synthon $C_{6}H_{6}\cdot C_{6}F_{6}$ Author Vanspeybroeck, Wim Herrebout, Wouter A. van der Veken, Benjamin J. Lundell, J. Perutz, R.N. Faculty/Department Faculty of Sciences. Chemistry Publication type article Publication 2003 Washington, D.C. , 2003 Subject Chemistry Source (journal) The journal of physical chemistry : B : materials, surfaces, interfaces and biophysical. - Washington, D.C., 1997, currens The journal of physical chemistry : B : condensed matter, materials, surfaces, interfaces and biophysical. - Washington, D.C. Volume/pages 107(2003) :50 , p. 13855-13861 ISSN 1520-6106 ISI 000187279200017 Carrier E Target language English (eng) Full text (Publishers DOI) Affiliation University of Antwerp Abstract The 1:1 complex between benzene and hexafluorobenzene has been studied in liquid krypton. Molecular dynamics simulations on the solutions predict that the lifetime of the complex varies between 33(20) ps at 126 K and 17(5) ps at 158 K, long enough to allow detection of the complex by infrared spectroscopy. Infrared spectroscopy in the 125-165 K temperature range of solutions in liquid krypton containing hexafluorobenzene and benzene, benzene-d(1), sym-benzene-d(3), or benzene-d(6) reveal the presence of bands due to the complex. From an analysis of the spectra as a function of temperature, the complexation enthalpy in solution was determined to be -6.0(2) kJ mol(-1). The liquid-phase complexation enthalpy was transformed into a gas-phase value of - 12.3 kJ mol(-1) by correcting for the solvent influences using free energy perturbation theory Monte Carlo simulations of the solutions. Ab initio calculations, at the MP2/6-31 G(d) level, predict a complexation energy of - 16.8 kJ mol(-1) and show that the complex has C-s symmetry with the two aromatic rings slightly shifted and tilted away from 6-fold symmetry. A critical comparison of the ab initio frequencies with experimentally observed complex bands confirms literature data on the failure of the out-of-plane force field for benzene at the ab initio level employed. E-info http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000187279200017&DestLinkType=RelatedRecords&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848 http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000187279200017&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848 http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000187279200017&DestLinkType=CitingArticles&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848 Handle