Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CNDO molecular orbital calculations have been performed to analyze donor-acceptor interactions between molecular chlorine and benzene, toluene, mesitylene and hexamethylbenzene and the, as yet, unreported chlorine-hexafluorobenzene and carbon disulfide-benzene pairs. The stabilization energy and the dipole moment and its derivative (∂p/∂RCICI) calculated for the benzene-chlorine complex are in good agreement with the estimated experimental values. The trends in the experimental stabilization energies and the Cl-Cl vibrational frequencies with increasing methyl substitution appear to be well reproduced by the calculations. The charge transferred from the benzene donor is polarized toward the outer chlorine atom or sulfur atom. For hexafluorobenzene-chlorine the direction of electronic charge polarization is reversed from that of the benzene and methylbenzene complexes. The calculated results are discussed within the framework of Muliiken's simplified resonance theory for complexes. © 1975.292211223CAPES; Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Mulliken, Person, (1969) Molecular Complexes, , John Wiley and Sons, New YorkHanna, (1968) J. Amer. Chem. Soc., 90, p. 285Hanna, Wlliams, (1968) J. Amer. Chem. Soc., 90, p. 5358Lippert, Hanna, Trotter, (1969) J. Amer. Chem. Soc., 91, p. 4035Person, (1973) Spectroscopy and Structure of Molecular Complexes, , J. Yarwood, Plenum Press, London, Chap. IClementi, (1967) J. Chem. Phys., 46, p. 3851Clementi, (1967) J. Chem. Phys., 47, p. 2323Clementi, Gayles, (1967) J. Chem. Phys., 47, p. 3837Carreira, Person, (1972) J. Amer. Chem. Soc., 94, p. 1485Pople, Beveridge, (1970) Approximate Molecular Orbital Theory, , McGraw Hill, New YorkChestnut, Wormer, The TCNE-benzene complex: A CNDO approach (1971) Theoretica Chimica Acta, 20, p. 250Nelander, (1972) Theor. Chim. Acta, 25, p. 382Tamres, (1964) J. Phys. Chem., 68, p. 2621a P.R. Dobosh, Quantum Chemistry Program Exchange, Department of Chemistry,Indiana University, Bloomington, Indiana, program No. 141b P.M. Kuznesof, QCPE program No. 94Pople, Segal, (1966) J. Chem. Phys., 44, p. 3289Santry, (1968) J. Amer. Chem. Soc., 90, p. 3309Mulliken, (1955) J. Chem. Phys., 23, p. 1833Mulliken, (1955) J. Chem. Phys., 23, p. 1841Mulliken, (1955) J. Chem. Phys., 23, p. 2338Mulliken, (1955) J. Chem. Phys., 23, p. 2343a P.R. Dobosh, Quantum Chemistry Program Exchange, Department of Chemistry,Indiana University, Bloomington, Indiana, program No. 141Ralston, (1965) A First Course in Numerical Analysis, p. 46. , McGraw-Hill, New YorkHassel, Stromme, Crystal Structure of the Addition Compound Benzene-Chlorine (1:1). (1959) Acta Chemica Scandinavica, 13, p. 1781Mulliken, (1952) J. Amer. Chem. Soc., 74, p. 811Brundle, Robin, Kueblen, (1972) J. Amer. Chem. Soc., 94, p. 1466Marschner, Goetz, (1973) Tetrahedron, 29, p. 3105Andrews, Keefer, (1952) J. Amer. Chem. Soc., 74, p. 4500Bhowmik, (1971) Spectrochim. Acta, Part A, 27, p. 321. , the effect of solvent on the formation constants and spectral properties of benzene-I2 and benzene and mesitylene—TCNE complexes has recently been examined byBhowmik, Srimani, (1973) Spectrochim. Acta, Part A, 29, p. 935Ferguson, Matsen, (1960) J. Amer. Chem. Soc., 82, p. 3268Kortüm, Walz, (1953) Z. Elektrochem., 7 R, p. 73. , report a much higher value of 1.80 D. Since the CNDO theory has overestimated the amount of charge transfer it seems more realistic to compare our calculated value of 1.12 D with the value of 0.72 DFleming, Hanna, Nuclear quadrupole resonance investigation of iodine monochloride complexed with pyridines (1971) Journal of the American Chemical Society, 93, p. 5030Bowmaker, Hacobian, Nuclear quadrupole resonance of charge-transfer complexes. II. The aminehalogen complexes (1969) Australian Journal of Chemistry, 22, p. 2047Klaboe, (1967) J. Amer. Chem. Soc., 89, p. 3667Rosen, Shen, Stenman, Raman study of iodine complexes in solutions (1971) Molecular Physics, 22, p. 33b P.M. Kuznesof, QCPE program No. 94Person, Erickson, Buckles, (1960) J. Amer. Chem. Soc., 82, p. 29Segal, Klein, (1967) J. Chem. Phys., 47, p. 4236Fredin, Nelander, (1974) J. Amer. Chem. Soc., 96, p. 1672Fredin, Nelander, On the structure of benzene halogen complexes (1974) Molecular Physics, 27, p. 885