Equilibrium isotope effects as a probe of nonbonding attractions.
The equilibrium isotope effects (EIEs) in the capsule complex (12 + p-xylene + CCl4) were computed with two simple models that mimic two types of contacts, -CH3.Ar and -CH3.CCl4. By using the MP2/6-311++G(d,p) method, the calculated equilibrium constants are consistent with the reported experimental data. Harmonic frequency analyses indicate that vibrational frequency changes caused by nonbonding attractions lead to the observed EIE.
Zhao
Yi-Lei
YL
Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA.
Houk
K N
KN
Rechavi
Dalit
D
Scarso
Alessandro
A
Rebek
Julius
J
D001554:Benzene / Q000737:chemistry*; D002251:Carbon Tetrachloride / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry; D041961:Deuterium Exchange Measurement / Q000379:methods*; D007700:Kinetics; D008697:Methane / Q000737:chemistry*; D008958:Models, Molecular; D013816:Thermodynamics; D014992:Xylenes / Q000737:chemistry*
D014992:Xylenes; D003903:Deuterium; D002251:Carbon Tetrachloride; D001554:Benzene; D008697:Methane