The electrostatic interactions in van der Waals complexes involving aromatic molecules

The minima in the electrostatic energy, for accessible orientations, have been located for the s‐tetrazine and benzene dimers and the 1:1 complexes of s‐tetrazine with hydrogen chloride, water, acetylene, and benzene, and of benzene with acetylene, anthracene, and perylene. The minima give reasonably successful predictions of the structures of these van der Waals molecules, demonstrating the importance of the electrostatic interactions in these systems. The electrostatic energy was calculated using sets of distributed multipoles obtained from ab initio wave functions of the monomers. This method is contrasted with empirical point charge and central multipole models for the electrostatic energy. It is shown that the simple models for the electrostatic interactions can give qualitatively misleading results for aromatic systems.

[1]  M. Alderton,et al.  Explicit formulae for the electrostatic energy, forces and torques between a pair of molecules of arbitrary symmetry , 1984 .

[2]  J. Pawliszyn,et al.  Interactions between aromatic systems: dimers of benzene and s-tetrazine , 1984 .

[3]  B. W. V. D. Waal,et al.  Computed structure of small benzene clusters , 1986 .

[4]  C. E. Dykstra,et al.  Electrical properties of ammonia and the structure of the ammonia dimer , 1986 .

[5]  Alistair P. Rendell,et al.  The validity of electrostatic predictions of the shapes of van der Waals dimers , 1985 .

[6]  Mass-selective two-color photoionization of benzene clusters , 1981 .

[7]  Sarah L. Price,et al.  A DISTRIBUTED MULTIPOLE ANALYSIS OF THE CHARGE-DENSITIES OF THE AZABENZENE MOLECULES , 1983 .

[8]  Patrick W. Fowler,et al.  Do electrostatic interactions predict structures of van der Waals molecules , 1983 .

[9]  C. Haynam,et al.  Spectroscopy and photophysics of organic clusters , 1982 .

[10]  Patrick W. Fowler,et al.  A model for the geometries of Van der Waals complexes , 1985 .

[11]  Alistair P. Rendell,et al.  The role of electrostatics in molecular interactions: prediction of shapes and electronic properties of weakly bound complexes , 1986 .

[12]  S. Oikawa,et al.  Growth mechanism of benzene clusters and crystalline benzene , 1985 .

[13]  Sarah L. Price,et al.  A distributed multipole analysis of the charge densities of some aromatic hydrocarbons , 1985 .

[14]  Serafin Fraga,et al.  A semiempirical formulation for the study of molecular interactions , 1982 .

[15]  A. M. Liquori,et al.  The structure of heterocyclic compounds containing nitrogen. I. Crystal and molecular structure of s‐tetrazine , 1956 .

[16]  J. Menapace,et al.  Supersonic molecular jet studies of the pyrazine and pyrimidine dimers , 1986 .

[17]  C. Haynam,et al.  Dimers in jet‐cooled s‐tetrazine vapor: Structure and electronic spectra , 1983 .

[18]  D. E. Williams,et al.  Calculated energy and conformation of clusters of benzene molecules and their relationship to crystalline benzene , 1980 .

[19]  J. Lisy,et al.  The assignment of cluster vibrational predissociation spectra by mass spectroscopic detection: The use of isotopes , 1986 .

[20]  M. Schauer,et al.  Calculations of the geometry and binding energy of aromatic dimers: Benzene, toluene, and toluene–benzene , 1985 .

[21]  E. W. Schlag,et al.  Spectra of isotopically mixed benzene dimers: Details on the interaction in the vdW bond , 1986 .

[22]  Anthony J. Stone,et al.  Distributed multipole analysis, or how to describe a molecular charge distribution , 1981 .

[23]  D. Millen,et al.  Determination of properties of hydrogen-bonded dimers by rotational spectroscopy and a classfication of dimer geometries , 1982 .

[24]  Mark Schauer,et al.  Dimers of aromatic molecules: (Benzene)2, (toluene)2, and benzene–toluene , 1984 .

[25]  Stephen M. Cohen,et al.  Spectroscopy of benzene complexes with perylene and other aromatic species , 1986 .

[26]  William Klemperer,et al.  Molecular beam studies of benzene dimer, hexafluorobenzene dimer, and benzene–hexafluorobenzene , 1979 .

[27]  Stephen J. Harris,et al.  Benzene dimer: A polar molecule , 1975 .

[28]  Thomas L. Starr,et al.  Calculation of the crystal structures of hydrocarbons by molecular packing analysis , 1977, Comput. Chem..

[29]  C. Haynam,et al.  Ultraviolet spectra of benzene clusters , 1981 .

[30]  Bruce J. Berne,et al.  Intermolecular potential models for anisotropic molecules, with applications to N2, CO2, and benzene , 1976 .

[31]  C. E. Dykstra,et al.  Electrical influence on monomer orientation in hydrogen bonded and other weakly bonded complexes , 1986 .

[32]  D. Levy,et al.  The multiphoton ionization spectrum of complexes of benzene and acetylene , 1985 .

[33]  R. O. Watts,et al.  Interactions between benzene molecules , 1976 .

[34]  D. Cruickshank,et al.  The crystal structure of benzene at — 3°C , 1958, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[35]  A. Stone,et al.  Electrostatic predictions of shapes and properties of Van der Waals molecules , 1986 .

[36]  A. Stone,et al.  Intermolecular forces in van der waals dimers , 1986 .