Validation and assessment of an accurate approach to the correlation problem in density functional theory: The Kriger–Chen–Iafrate–Savin model

In the present paper, we validate and assess a correlation functional based on the so-called meta generalized gradient approximation, whose form and parameters are entirely derived only from first-principles criteria. In particular, we have carried out a detailed comparison with the most common, parametrized correlation functionals. Next, we propose a new model in which the correlation functional proposed by Kriger, Chen, Iafrate, and Savin is integrated in a hybrid Hartree–Fock/density functional theory scheme. In such approach only one, or two in the G2-optimized version, parameters are adjusted on experimental data, all the others being derived from purely theoretical considerations. The results obtained for a set of molecular properties, including H-bonded complexes, proton transfer model, SN2 reaction and magnetic properties, are satisfactory and comparable, if not better, with those delivered by the most common functionals including heavy parametrization. The way in which the whole functional is der...

[1]  Vincenzo Barone,et al.  Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models , 1998 .

[2]  Martin Quack,et al.  On hydrogen-bonded complexes: the case of (HF)2 , 1996 .

[3]  Axel D. Becke,et al.  Density functionals from the extended G2 test set: Second-order gradient corrections , 1998 .

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

[5]  J. W. Larson,et al.  Hydrogen bonding in gas-phase anions. An experimental investigation of the interaction between chloride ion and Broensted acids from ion cyclotron resonance chloride exchange equilibriums , 1984 .

[6]  G. Scuseria,et al.  A new correlation functional based on analysis of the Colle–Salvetti functional , 2002 .

[7]  Dennis R. Salahub,et al.  New τ-dependent correlation functional combined with a modified Becke exchange , 2000 .

[8]  A. Daniel Boese,et al.  Predicting the binding energies of H-bonded complexes: A comparative DFT study , 1999 .

[9]  K. Hirao,et al.  Parameter-free exchange functional , 2000 .

[10]  A. Rappé,et al.  Ab Initio Calculation of Nonbonded Interactions: Are We There Yet? , 2000 .

[11]  J. Wolff.  Theoretical Aspects of Physical Organic Chemistry. The SN2 Mechanism. Von S. S. Shaik, H. B. Schlegel, und S. Wolfe. Wiley, New York, 1992. XV, 285 S., geb. 47.50$. ‐ ISBN 0–471–84041–6 , 1993 .

[12]  Andreas Savin,et al.  Virtual space level shifting and correlation energies , 1998 .

[13]  W. Weltner.  Magnetic atoms and molecules , 1983 .

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

[15]  Kimihiko Hirao,et al.  A NEW ONE-PARAMETER PROGRESSIVE COLLE-SALVETTI-TYPE CORRELATION FUNCTIONAL , 1999 .

[16]  Vincenzo Barone,et al.  Proton transfer in the ground and lowest excited states of malonaldehyde: A comparative density functional and post‐Hartree–Fock study , 1996 .

[17]  V. Barone,et al.  An accurate density functional method for the study of magnetic properties: the PBE0 model , 1999 .

[18]  Davidson,et al.  Ground-state correlation energies for atomic ions with 3 to 18 electrons. , 1993, Physical review. A, Atomic, molecular, and optical physics.

[19]  L. Radom,et al.  The performance of B3-LYP density functional theory in describing SN2 reactions at saturated carbon , 1996 .

[20]  Benny G. Johnson,et al.  The performance of a family of density functional methods , 1993 .

[21]  Gustavo E. Scuseria,et al.  A novel form for the exchange-correlation energy functional , 1998 .

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

[23]  Tom Ziegler,et al.  Potential Energy Surfaces of the Gas-Phase SN2 Reactions X- + CH3X = XCH3 + X- (X = F, Cl, Br, I): A Comparative Study by Density Functional Theory and ab Initio Methods , 1994 .

[24]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[25]  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 .

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

[27]  Nicholas C. Handy,et al.  Assessment of a new local exchange functional OPTX , 2001 .

[28]  Ranbir Singh,et al.  J. Mol. Struct. (Theochem) , 1996 .

[29]  Giovanni Vignale,et al.  Electronic density functional theory : recent progress and new directions , 1998 .

[30]  Carlo Adamo,et al.  Predicting proton transfer barriers with density functional methods , 1999 .

[31]  D. Chong.  Recent Advances in Density Functional Methods Part III , 2002 .

[32]  John P. Perdew,et al.  Accurate Density Functional with Correct Formal Properties: A Step Beyond the Generalized Gradient Approximation , 1999 .

[33]  Axel D. Becke,et al.  On the large‐gradient behavior of the density functional exchange energy , 1986 .

[34]  Vincenzo Barone,et al.  Physically motivated density functionals with improved performances: The modified Perdew–Burke–Ernzerhof model , 2002 .

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

[36]  Renato Colle,et al.  Approximate calculation of the correlation energy for the closed shells , 1975 .

[37]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[38]  S. Patchkovskii,et al.  Improving ``difficult'' reaction barriers with self-interaction corrected density functional theory , 2002 .

[39]  K. Burke,et al.  Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] , 1997 .

[40]  Vincenzo Barone,et al.  Validation of self‐consistent hybrid density functionals for the study of structural and electronic characteristics of organic π radicals , 1995 .

[41]  Thanh N. Truong,et al.  Hydration effects on reaction profiles: an ab initio dielectric continuum study of the SN2 Cl- + CH3Cl reaction , 1995 .

[42]  Axel D. Becke,et al.  Optimized density functionals from the extended G2 test set , 1998 .

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

[44]  T. R. Dyke,et al.  Partially deuterated water dimers: Microwave spectra and structure , 1980 .

[45]  J. Perdew,et al.  Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation. , 1986, Physical review. B, Condensed matter.

[46]  Krishnan Raghavachari,et al.  Gaussian‐1 theory of molecular energies for second‐row compounds , 1990 .

[47]  Axel D. Becke,et al.  A new inhomogeneity parameter in density-functional theory , 1998 .

[48]  John P. Perdew,et al.  Molecular and solid‐state tests of density functional approximations: LSD, GGAs, and meta‐GGAs , 1999 .

[49]  G. Chan,et al.  An extensive study of gradient approximations to the exchange-correlation and kinetic energy functionals , 2000 .

[50]  V. Barone,et al.  Proton transfer in model hydrogen-bonded systems by a density functional approach , 1994 .

[51]  Jianmin Tao,et al.  An accurate MGGA-based hybrid exchange-correlation functional , 2002 .

[52]  L. Curtiss,et al.  Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation , 1997 .

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

[54]  M. Frisch,et al.  Gaussian 94 user's reference , 1996 .

[55]  Vincenzo Barone,et al.  Toward reliable adiabatic connection models free from adjustable parameters , 1997 .

[56]  Wolfram Koch,et al.  A Chemist's Guide to Density Functional Theory , 2000 .

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