Development and assessment of new exchange-correlation functionals

We recently presented a new method for developing generalized gradient approximation (GGA) exchange-correlation energy functionals, using a least-squares procedure involving numerical exchange-correlation potentials and experimental energetics and nuclear gradients. In this paper we use the same method to develop a new GGA functional, denoted HCTH, based on an expansion recently suggested by Becke [J. Chem. Phys. 107, 8554 (1997)]. For our extensive training set, the new functional yields improved energetics compared to both the BLYP and B3LYP functionals [Phys. Rev. A 38, 3098 (1988); Phys. Rev. B 37, 785 (1988); J. Chem. Phys. 98, 5648 (1993); J. Phys. Chem. 98, 11623 (1994)]. The geometries of these systems, together with those of a set of transition metal compounds, are shown to be an improvement over the BLYP functional, while the reaction barriers for six hydrogen abstraction reactions are comparable to those of B3LYP. These improvements are achieved without introducing any fraction of exact orbital...

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

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

[3]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[4]  D L Diedrich,et al.  An Accurate Quantum Monte Carlo Calculation of the Barrier Height for the Reaction H + H2 → H2 + H , 1992, Science.

[5]  R. Wheeler,et al.  Study of hydrogen abstraction reactions by density-functional methods , 1997 .

[6]  D. Dixon,et al.  Ab initio prediction of the barrier height for abstraction of H from CH4 by OH , 1993 .

[7]  A. Wachters,et al.  Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms , 1970 .

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

[9]  P. Jeffrey Hay,et al.  Gaussian basis sets for molecular calculations. The representation of 3d orbitals in transition‐metal atoms , 1977 .

[10]  William A. Goddard,et al.  Theoretical studies of a hydrogen abstraction tool for nanotechnology , 1991 .

[11]  G. A. Petersson,et al.  Transition states for chemical reactions I. Geometry and classical barrier height , 1998 .

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

[13]  Pedro Pedro Gili= Pedro Gili Trujillo Gili,et al.  Exploring chromium (VI) dioxodihalides chemistry: Is density functional theory the most suitable tool? , 1996 .

[14]  Parr,et al.  From electron densities to Kohn-Sham kinetic energies, orbital energies, exchange-correlation potentials, and exchange-correlation energies. , 1994, Physical review. A, Atomic, molecular, and optical physics.

[15]  Nicholas C. Handy,et al.  Development of New Exchange-Correlation Functionals. 2 , 1998 .

[16]  Nicholas C. Handy,et al.  The development of new exchange-correlation functionals , 1998 .

[17]  H. Stoll,et al.  Correlation energies in the spin-density functional formalism , 1980 .

[18]  W. Thiel,et al.  Exchange-correlation density functional beyond the gradient approximation , 1998 .

[19]  J. Perdew,et al.  Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy , 1982 .

[20]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[21]  A. Becke.  Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals , 1997 .

[22]  Kieron Burke,et al.  Comparison shopping for a gradient-corrected density functional , 1996 .

[23]  J. Gauss,et al.  Accurate coupled cluster reaction enthalpies and activation energies for X+H2→XH+H (X=F, OH, NH2, and CH3) , 1993 .

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