Abinitio second‐ and fourth‐order Mo/ller–Plesset study on structure, stabilization energy, and stretching vibration of benzene⋅⋅⋅X (X=He,Ne,Ar,Kr,Xe) van der Waals molecules

The C6v structure of benzene⋅⋅⋅X (X=He, Ne, Ar, Kr, Xe) complexes was investigated with second‐order Mo/ller–Plesset (MP2) theory; for the benzene⋅⋅⋅He the whole potential‐energy surface (PES) was also studied. The stabilization energy of the benzene⋅⋅⋅He was also determined at the fourth‐order Mo/ller–Plesset (MP4) level; the respective MP4 stabilization energy is almost identical with MP2 stabilization energy which is due to the compensation of MP3 and MP4 contributions. The ab initio MP2 intermolecular distances agree nicely for all the complexes studied with the experimental value. While the stabilization energy of benzene⋅⋅⋅He and benzene⋅⋅⋅Ne (67 cm−1; 99 cm−1) is considerably smaller than that of benzene⋅⋅⋅Ar (429 cm−1), the intersystem distance differs less (3.32 A, 3.50 A, 3.53 A). The stabilization energies and intersystem distances for benzene⋅⋅⋅Kr and benzene⋅⋅⋅Xe are 485 and 601 cm−1 and 3.71 and 3.89 A, respectively. The PES of benzene⋅⋅⋅He differs from that of benzene⋅⋅⋅Ar and can be charac...

[1]  Timothy Clark,et al.  Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F , 1983 .

[2]  E. Riedle,et al.  Rotationally resolved ultraviolet spectrum of the benzene–Ar complex by mass‐selected resonance‐enhanced two‐photon ionization , 1990 .

[3]  Floppy structure of the benzene dimer: Ab initio calculation on the structure and dipole moment , 1990 .

[4]  H. Krause,et al.  Metastable decay and binding energies of van der Waals cluster ions , 1991 .

[5]  J. Menapace,et al.  Calculation of the Vibronic Structure of Solute/Solvent van der Waals Clusters. , 1987 .

[6]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[7]  E. Riedle,et al.  Van der Waals bond lengths and electronic spectral shifts of the benzene---Kr and benzene---Xe complexes , 1991 .

[8]  Pavel Hobza,et al.  Intermolecular interactions between medium-sized systems. Nonempirical and empirical calculations of interaction energies. Successes and failures , 1988 .

[9]  P. Hobza,et al.  Ab initio Calculations on the Structure, Stabilization, and Dipole-Moment of Benzene ... Ar Complex , 1991 .

[10]  L. Kroon-Batenburg,et al.  The use of a moment-optimized DZP basis set for describing the interaction in the water dimer , 1985 .

[11]  J. Simons,et al.  Mo/ller–Plesset perturbation theory for van der Waals complexes bound by electron correlation effects: Ground states of the Ar and Mg dimers , 1987 .

[12]  S. Leutwyler,et al.  The adsorption of rare-gas atoms on microsurfaces of large aromatic molecules , 1987 .

[13]  J. Pople,et al.  Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules , 1972 .

[14]  J. Simons,et al.  Van der Waals minima in excited states by Møller-Plesset perturbation theory: The a 3Σu+ State of He2 And the 3π state of MgHe , 1988 .

[15]  K. Jordan,et al.  Theoretical investigation of the a 3Σ+u, A 1Σ+u, c 3Σ+g, and C 1Σ+g potential energy curves of He2 and of He*(2 1S, 2 3S)+He scattering , 1983 .

[16]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi , 1985 .

[17]  Joshua Jortner,et al.  Large van der Waals ions , 1983 .

[18]  D. L. Monts,et al.  Rotational analysis of the 1B2u(ππ) ←1A1g, (610) band of benzene and helium–benzene van der Waals complexes in a supersonic jet , 1979 .

[19]  M. Klobukowski,et al.  Model potential study of the interactions in Ar2, Kr2 and Xe2 dimers , 1984 .

[20]  M. Su,et al.  A fluorescence characterization of the p-difluorobenzene-argon van der Waals complex. Energy levels, geometries and dissociation energies , 1991 .

[21]  J. Andzelm,et al.  Reliable Gaussian basis sets for closed‐shell atoms , 1987 .