Interaction energies of van der Waals and hydrogen bonded systems calculated using density functional theory: Assessing the PW91 model

The performance of density functional theory using the Perdew and Wang’s exchange and correlation functionals (PW91) functional for the prediction of intermolecular interactionenergies is evaluated based on calculations on the neon, argon, methane, ethylene, and benzene dimers, as well as on 12 hydrogen bonded complexes (water, methanol, formic acid, hydrogen fluoride, ammonia, formamide dimers and water–methanol, water–dimethyl ether, water–formaldehyde, hydrogen cyanide–hydrogen fluoride, water–ammonia, water–formamide complexes). The results were compared with those obtained from Becke’s exchange and Lee, Yang, and Parr’s correlation functionals (BLYP), Becke’s 3 parameter functional combined with Lee, Yang, and Parr’s correlation functional (B3LYP), second order Mo/ller–Plesset perturbation (MP2), and coupled cluster calculations with single and double substitutions and with non-iterative triple corrections [CCSD(T)] calculations. The calculated interactionenergies show that the PW91 functional performs much better than the BLYP or B3LYP functionals. The error in the computed binding energies of the hydrogen bonded complexes is 20% in the worst case. The most demanding cases are the systems with large dispersion contributions to the binding energy, such as the benzene dimer. In contrast to the BLYP and B3LYP functionals which fail to account for dispersion, the PW91 functional at least partly recovers the attraction. The basis set dependence of the PW91 functionals is relatively small in contrast to the MP2 and CCSD(T) methods. Despite its occasional difficulties with dispersion interaction, the PW91 functional may be a viable alternative to the ab initio methods, certainly in situations where large complexes are being studied.

[1]  Jae Shin Lee,et al.  Ab initio study of (NH3)2: Accurate structure and energetics , 2000 .

[2]  Masuhiro Mikami,et al.  Effects of basis set and electron correlation on the calculated interaction energies of hydrogen bonding complexes: MP2/cc-pV5Z calculations of H2O–MeOH,H2O–Me2O,H2O–H2CO, MeOH–MeOH, and HCOOH–HCOOH complexes , 1999 .

[3]  Laszlo Nemes,et al.  Tunnelling lifetimes of the rovibronic levels in the B electronic state of the CH radical obtained from ab initio data , 1999 .

[4]  Á. Pérez‐Jiménez,et al.  Density-functional study of van der Waals forces on rare-gas diatomics: Hartree–Fock exchange , 1999 .

[5]  M. Quack,et al.  HF dimer: Empirically refined analytical potential energy and dipole hypersurfaces from ab initio calculations , 1998 .

[6]  A NEW AB INITIO BASED MODEL POTENTIAL FOR METHANE , 1998 .

[7]  S. Tsuzuki,et al.  Intermolecular interaction potentials of methane and ethylene dimers calculated with the Møller–Plesset, coupled cluster and density functional methods , 1998 .

[8]  Masuhiro Mikami,et al.  NEW MEDIUM-SIZE BASIS SETS TO EVALUATE THE DISPERSION INTERACTION OF HYDROCARBON MOLECULES , 1998 .

[9]  Yingkai Zhang,et al.  Describing van der Waals interaction in diatomic molecules with generalized gradient approximations: The role of the exchange functional , 1997 .

[10]  Mark R. Pederson,et al.  Application of the generalized-gradient approximation to rare-gas dimers , 1997 .

[11]  Jacques Weber,et al.  Comparative Study of Benzene···X (X = O2, N2, CO) Complexes Using Density Functional Theory: The Importance of an Accurate Exchange−Correlation Energy Density at High Reduced Density Gradients , 1997 .

[12]  J. Šponer,et al.  MP2 and CCSD(T) study on hydrogen bonding, aromatic stacking and nonaromatic stacking , 1997 .

[13]  Pavel Hobza,et al.  Potential Energy Surface for the Benzene Dimer. Results of ab Initio CCSD(T) Calculations Show Two Nearly Isoenergetic Structures: T-Shaped and Parallel-Displaced , 1996 .

[14]  Michiel Sprik,et al.  A density‐functional study of the intermolecular interactions of benzene , 1996 .

[15]  Richard L. Jaffe,et al.  A quantum chemistry study of benzene dimer , 1996 .

[16]  Masuhiro Mikami,et al.  Basis set effects on the calculated bonding energies of neutral benzene dimers: importance of diffuse polarization functions , 1996 .

[17]  David Feller,et al.  Hydrogen bond energy of the water dimer , 1996 .

[18]  J. Šponer,et al.  Density functional theory and molecular clusters , 1995, Journal of Computational Chemistry.

[19]  José M. Pérez-Jordá,et al.  A density-functional study of van der Waals forces: rare gas diatomics. , 1995 .

[20]  M. Szczęśniak,et al.  Origins of Structure and Energetics of van der Waals Clusters from ab Initio Calculations , 1994 .

[21]  Peter Pulay,et al.  CAN (SEMI) LOCAL DENSITY FUNCTIONAL THEORY ACCOUNT FOR THE LONDON DISPERSION FORCES , 1994 .

[22]  Kazutoshi Tanabe,et al.  Basis set effects on the intermolecular interaction of hydrocarbon molecules obtained by an ab initio molecular orbital method : evaluation of dispersion energy , 1994 .

[23]  Pavel Hobza,et al.  Potential Energy Surface of the Benzene Dimer: Ab Initio Theoretical Study , 1994 .

[24]  Kazutoshi Tanabe,et al.  Refinement of Nonbonding Interaction Potential Parameters for Methane on the Basis of the Pair Potential Obtained by MP3/6-311G(3d,3p)-Level ab Initio Molecular Orbital Calculations: The Anisotropy of H/H Interaction , 1994 .

[25]  D. Lacks,et al.  Pair interactions of rare-gas atoms as a test of exchange-energy-density functionals in regions of large density gradients. , 1993, Physical review. A, Atomic, molecular, and optical physics.

[26]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[27]  J. F. Ogilvie,et al.  Potential-energy functions of diatomic molecules of the noble gases , 1993 .

[28]  Kazutoshi Tanabe,et al.  Nonbonding interaction potential of ethylene dimer obtained from ab initio molecular orbital calculations : prediction of a D2d structure , 1992 .

[29]  J. F. Ogilvie,et al.  Potential-energy functions of diatomic molecules of the noble gases I. Like nuclear species , 1992 .

[30]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[31]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[32]  David Feller,et al.  Application of systematic sequences of wave functions to the water dimer , 1992 .

[33]  Alexander D. MacKerell,et al.  Importance of attractive van der Waals contribution in empirical energy function models for the heat of vaporization of polar liquids , 1991 .

[34]  Christopher A. Hunter,et al.  The nature of .pi.-.pi. interactions , 1990 .

[35]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[36]  S. Stolte,et al.  IR Excitation and dissociation of (NH3)n, (n = 2, 3, 4, 5) and ArNH3 , 1988 .

[37]  T. Pertsch,et al.  Infrared photodissociation of size-selected small ammonia clusters , 1988 .

[38]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[39]  Patrick W. Fowler,et al.  Theoretical studies of van der Waals molecules and intermolecular forces , 1988 .

[40]  L. A. Curtiss,et al.  Thermodynamic properties of gas-phase hydrogen-bonded complexes , 1988 .

[41]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[42]  Martin Head-Gordon,et al.  Quadratic configuration interaction. A general technique for determining electron correlation energies , 1987 .

[43]  John W. Bevan,et al.  Determination of dissociation energies and thermal functions of hydrogen-bond formation using high resolution FTIR spectroscopy , 1987 .

[44]  Sarah L. Price,et al.  The electrostatic interactions in van der Waals complexes involving aromatic molecules , 1987 .

[45]  Giles Henderson.  Heat of dimerization of formic acid by FTIR , 1987 .

[46]  Alan S. Pine,et al.  Hydrogen bond energies of the HF and HCl dimers from absolute infrared intensities , 1986 .

[47]  William L. Jorgensen,et al.  Optimized intermolecular potential functions for liquid hydrocarbons , 1984 .

[48]  J. Pople,et al.  Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions , 1980 .

[49]  Larry A. Curtiss,et al.  Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity , 1979 .

[50]  John A. Pople,et al.  Approximate fourth-order perturbation theory of the electron correlation energy , 1978 .

[51]  G. Matthews,et al.  An intermolecular pair potential energy function for methane , 1976 .

[52]  Hans-Joachim Werner,et al.  PNO-CI and PNO-CEPA studies of electron correlation effects , 1976 .

[53]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

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

[55]  N. Bridge,et al.  The polarization of laser light scattered by gases , 1964, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[56]  J. Prausnitz,et al.  Intermolecular Potential Functions and the Second and Third Virial Coefficients , 1964 .

[57]  Bernard J. Ransil,et al.  Studies in Molecular Structure. IV. Potential Curve for the Interaction of Two Helium Atoms in Single‐Configuration LCAO MO SCF Approximation , 1961 .

[58]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .