On decomposition of second‐order Mo/ller–Plesset supermolecular interaction energy and basis set effects

The basis set effects on the total self‐consistent field (SCF) and second‐order Mo/ller–Plesset (MP2) interaction energies in the HF dimer (in the equilibrium geometry) are investigated in relation to their components: electrostatic, exchange, induction, and dispersion, calculated within the framework of intermolecular Mo/ller–Plesset perturbation theory (IMPPT). The basis set dependence of the SCF interaction energy in the HF dimer is almost exactly determined by the electrostatic contribution. The exchange, induction, and the SCF‐deformation terms are found substantially less sensitive. The MP2 correlation contribution reflects primarily the basis set dependence of dispersion. However, an accurate image of the basis set dependence is reproduced only if the electrostatic‐correlation term is considered as well. Other correlation contributions: the deformation‐ correlation and exchange terms are found to be much less sensitive to basis set effects. All these conclusions are valid only under the condition t...

[1]  S. Scheiner,et al.  Correction of the basis set superposition error in SCF and MP2 interaction energies. The water dimer , 1986 .

[2]  M. Gutowski,et al.  Effective basis sets for calculations of exchange‐repulsion energy , 1984 .

[3]  G. Diercksen,et al.  Interactions in the halide ion-rare gas systems: The F−…He interaction potential , 1989 .

[4]  A. J. Sadlej.  Long range induction and dispersion interactions between Hartree-Fock subsystems , 1980 .

[5]  M. Jaszuński.  Coupled Hartree-Fock calculation of the induction energy , 1980 .

[6]  M. Gutowski,et al.  Dimer centred basis set in the calculations of the first-order interaction energy with CI wavefunction , 1985 .

[7]  U. Kaldor,et al.  Many-Body Methods in Quantum Chemistry , 1989 .

[8]  M. Gutowski,et al.  The impact of higher polarization functions of second-order dispersion energy. Partial wave expansion and damping phenomenon for He2☆ , 1987 .

[9]  G. Chałasiński.  Perturbation calculations of the interaction energy between closed-shell Hartree-Fock atoms , 1983 .

[10]  David Feller,et al.  One‐electron properties of several small molecules using near Hartree–Fock limit basis sets , 1987 .

[11]  K. Szalewicz,et al.  Symmetry-adapted double-perturbation analysis of intramolecular correlation effects in weak intermolecular interactions , 1979 .

[12]  Rodney J. Bartlett,et al.  Analytic energy derivatives in many‐body methods. I. First derivatives , 1989 .

[13]  G. Karlström,et al.  Basis set superposition effects on properties of interacting systems. Dipole moments and polarizabilities , 1982 .

[14]  S. Scheiner,et al.  Analysis of the potential energy surface of Ar–NH3 , 1989 .

[15]  J. Maruani.  Molecules in Physics, Chemistry, and Biology , 1988 .

[16]  Maciej Gutowski,et al.  Weak interactions between small systems. Models for studying the nature of intermolecular forces and challenging problems for ab initio calculations , 1988 .

[17]  R. Amos.  Corrections to molecular one-electron properties using møller-plesset perturbation theory , 1980 .

[18]  C. Ghio,et al.  Effect of counterpoise corrections on the components of the interaction energy in the formate-, acetate-, and phosphate-water dimers: a study of basis set effects , 1989 .

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

[20]  Krzysztof Szalewicz,et al.  Intraatomic correlation effects for the He–He dispersion and exchange–dispersion energies using explicitly correlated Gaussian geminals , 1987 .

[21]  L. Curtiss,et al.  Gaussian‐1 theory: A general procedure for prediction of molecular energies , 1989 .

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

[23]  H. Schaefer,et al.  Extensive theoretical studies of the hydrogen‐bonded complexes (H2O)2, (H2O)2H+, (HF)2, (HF)2H+, F2H−, and (NH3)2 , 1986 .

[24]  B. Jeziorski,et al.  Variation-perturbation treatment of the hydrogen bond between water molecules , 1976 .

[25]  W. Kutzelnigg.  The ‘‘primitive’’ wave function in the theory of intermolecular interactions , 1980 .

[26]  J. V. Lenthe,et al.  An analysis of the partial wave expansion of the dispersion energy for Ne2 , 1984 .

[27]  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 .

[28]  C. E. Dykstra,et al.  Improved counterpoise corrections for the abinitio calculation of hydrogen bonding interactions , 1986 .

[29]  L. Piela,et al.  Interpretation of the Hartree-Fock interaction energy between closed-shell systems , 1988 .

[30]  J. Murrell,et al.  The dependence of exchange and coulomb energies on wave functions of the interacting systems , 1972 .

[31]  Jiří Čížek,et al.  Direct calculation of the Hartree–Fock interaction energy via exchange–perturbation expansion. The He … He interaction , 1987 .

[32]  T. W. Dingle,et al.  Contraction of the well‐tempered Gaussian basis sets: The first‐row diatomic molecules , 1989 .

[33]  P. Claverie.  Theory of intermolecular forces. I. On the inadequacy of the usual Rayleigh‐Schrödinger perturbation method for the treatment of intermolecular forces , 1971 .

[34]  Poul Jørgensen,et al.  Geometrical derivatives of energy surfaces and molecular properties , 1986 .

[35]  D. Truhlar,et al.  Erratum: Systematic study of basis set superposition errors in the calculated interaction energy of two HF molecules [J. Chem. Phys. 82, 2418 (1985)] , 1986 .

[36]  J. Collins,et al.  The full versus the virtual counterpoise correction for basis set superposition error in self-consistent field calculations , 1986 .

[37]  G. Chałasiński.  Exchange dispersion effect in the interaction between HF molecules , 1982 .

[38]  S. Scheiner,et al.  Primary and secondary basis set superposition error at the SCF and MP2 levels. H3N‐‐Li+ and H2O‐‐Li+ , 1987 .

[39]  L. Piela,et al.  Does the boys and bernardi function counterpoise method actually overcorrect the basis set superposition error , 1986 .

[40]  V. Kellö,et al.  Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties , 1991 .

[41]  S. J. Cole,et al.  A theoretical study of the water dimer interaction , 1988 .

[42]  J. Pople,et al.  Møller–Plesset theory for atomic ground state energies , 1975 .

[43]  H. Lischka,et al.  Coupled pair functional study on the hydrogen fluoride dimer. I. Energy surface and characterization of stationary points , 1988 .

[44]  M. Szczęśniak,et al.  On the connection between the supermolecular Møller-Plesset treatment of the interaction energy and the perturbation theory of intermolecular forces , 1988 .

[45]  S. Tolosa,et al.  A proposal for avoiding overestimation in the counterpoise basis set superposition error. Application to diatomic van der Waals systems , 1988 .

[46]  G. Diercksen,et al.  Finite-field many-body perturbation theory IV. Basis set optimization in MBPT calculations of molecular properties. Molecular quadrupole moments , 1983 .