Application of 25 density functionals to dispersion-bound homomolecular dimers

Abstract The ability of 25 density functional theory (DFT) methods to treat Ne2, Ar2, (CH4)2, (C2H4)2 and three conformations of the benzene dimer was studied. Only PW91, HTCH407, and VSXC predict all dimers to be bound. However, VSXC strongly over-binds all of the complexes. The DFTs predict repulsive potential energy surfaces (PES) for parallel benzene at large separations, in contrast to MP2. VSXC, B1B95, BB95, and BB1K, and to a lesser extent OLYP and O3LYP, are sensitive to the size of the integration grid used. When used with standard grids, these methods predict multiple minima on one or more dimer PESs.

[1]  Axel D. Becke,et al.  Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing , 1996 .

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

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

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

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

[6]  A. Daniel Boese,et al.  A new parametrization of exchange–correlation generalized gradient approximation functionals , 2001 .

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

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

[9]  Hans Peter Lüthi,et al.  Interaction energies of van der Waals and hydrogen bonded systems calculated using density functional theory: Assessing the PW91 model , 2001 .

[10]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

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

[12]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

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

[14]  David J. Tozer,et al.  Hybrid exchange-correlation functional determined from thermochemical data and ab initio potentials , 2001 .

[15]  Peter M. W. Gill,et al.  A new gradient-corrected exchange functional , 1996 .

[16]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[17]  Edward F. Valeev,et al.  Estimates of the Ab Initio Limit for π−π Interactions: The Benzene Dimer , 2002 .

[18]  N. Handy,et al.  Left-right correlation energy , 2001 .

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

[20]  Marvin L. Cohen,et al.  Electronic structure of solids , 1984 .

[21]  Michiel Sprik,et al.  New generalized gradient approximation functionals , 2000 .

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

[23]  Donald G. Truhlar,et al.  Adiabatic connection for kinetics , 2000 .

[24]  Fred A. Hamprecht,et al.  Development and assessment of new exchange-correlation functionals , 1998 .

[25]  Donald G. Truhlar,et al.  Development and Assessment of a New Hybrid Density Functional Model for Thermochemical Kinetics , 2004 .