Can contemporary density functional theory yield accurate thermodynamics for hydrogen bonding

Abstract Thermodynamic characteristics of dimerization were calculated for six molecules (including water, alcohols, and carboxylic acids) using density functional theory (DFT) methods and compared to corresponding experimental data. Basis set superposition error for different basis sets including polarization and diffuse Gaussian functions was calculated using the full counterpoise procedure. Ten out of twelve thermodynamic dimerization characteristics calculated with DZVPD/TZVPD basis sets agree with one of the available experimental values with near chemical accuracy (≈ 1 kcal/mol). It is concluded that DFT/DZVPD/TZVPD calculations can yield not only accurate molecular dipole moments, but also rather accurate thermodynamics of hydrogen bonding.

[1]  P. C. Hariharan,et al.  A self-consistent field interaction energy decomposition study of 12 hydrogen-bonded dimers , 1983 .

[2]  K. P. Murphy,et al.  Thermodynamics of structural stability and cooperative folding behavior in proteins. , 1992, Advances in protein chemistry.

[3]  B Honig,et al.  Free energy balance in protein folding. , 1995, Advances in protein chemistry.

[4]  Michael A. Bukatin,et al.  Incorporation of reaction field effects into density functional calculations for molecules of arbitrary shape in solution , 1994 .

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

[6]  Sarah L. Price,et al.  A TRANSFERABLE DISTRIBUTED MULTIPOLE MODEL FOR THE ELECTROSTATIC INTERACTIONS OF PEPTIDES AND AMIDES , 1990 .

[7]  P. C. Hariharan,et al.  Nonempirical Atom‐Atom Potentials for Main Components of Intermolecular Interaction Energy , 1986 .

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

[9]  K. Merz,et al.  Analysis of a large data base of electrostatic potential derived atomic charges , 1992 .

[10]  Dennis R. Salahub,et al.  Gaussian density functional calculations on hydrogen-bonded systems , 1992 .

[11]  Clifford E. Dykstra,et al.  Electrostatic interaction potentials in molecular force fields , 1993 .

[12]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[13]  M Karplus,et al.  The contribution of vibrational entropy to molecular association. The dimerization of insulin. , 1994, Journal of molecular biology.

[14]  P. Kollman,et al.  An all atom force field for simulations of proteins and nucleic acids , 1986, Journal of computational chemistry.

[15]  K. Dill.  Dominant forces in protein folding. , 1990, Biochemistry.

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

[17]  C. Mijoule,et al.  Density functional theory applied to proton-transfer systems. A numerical test , 1993 .

[18]  A. Rashin,et al.  Aspects of protein energetics and dynamics. , 1993, Progress in biophysics and molecular biology.

[19]  Stanley K. Burt,et al.  Molecular dipole moments calculated with density functional theory , 1994 .

[20]  Mark A. Spackman.  A simple quantitative model of hydrogen bonding. Application to more complex systems , 1987 .

[22]  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 .