A density functional study of van der Waals interactions

The applicability of density functional theory(DFT) to van der Waals (vdW) calculations are investigated by using the long-range exchange correction scheme and the Andersson–Langreth–Lundqvist vdW functional. By calculating bond energy potentials of rare-gas dimers, it was found that the present scheme gives much more accurate potentials for all dimers than conventional sophisticated DFT methods do. We therefore confirmed that vdW bonds are constructed under the balance of long-range exchange and vdW correlation interactions, although neither of these interactions are usually contained in pure exchange–correlation functionals. It was also found that calculated vdW potentials are obviously affected by functional forms for rapidly varying densities. Especially in vdW calculations, we must employ a correlation functional that satisfies the fundamental condition for rapidly varying density.

[1]  A. D. McLean,et al.  Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 , 1980 .

[2]  Michael J. Frisch,et al.  Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets , 1984 .

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

[4]  Ross D. Adamson,et al.  Efficient calculation of short‐range Coulomb energies , 1999 .

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

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

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

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

[9]  Kimihiko Hirao,et al.  A reexamination of exchange energy functionals , 1999 .

[10]  D. Langreth,et al.  Van Der Waals Interactions In Density Functional Theory , 2007 .

[11]  Ashcroft,et al.  Fluctuation attraction in condensed matter: A nonlocal functional approach. , 1991, Physical review. B, Condensed matter.

[12]  Andreas Savin,et al.  Combining long-range configuration interaction with short-range density functionals , 1997 .

[13]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

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

[15]  K. Hirao,et al.  A long-range correction scheme for generalized-gradient-approximation exchange functionals , 2001 .

[16]  Manfred Lein,et al.  Toward the description of van der Waals interactions within density functional theory , 1999, J. Comput. Chem..

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

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

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

[20]  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 .

[21]  R. Dreizler,et al.  Density Functional Theory: An Approach to the Quantum Many-Body Problem , 1991 .

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

[23]  J. C. Slater A Simplification of the Hartree-Fock Method , 1951 .

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

[25]  A. Bondi van der Waals Volumes and Radii , 1964 .

[26]  Ashok Kumar,et al.  Pseudo-spectral dipole oscillator strengths and dipole-dipole and triple-dipole dispersion energy coefficients for HF, HCl, HBr, He, Ne, Ar, Kr and Xe , 1985 .

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

[28]  Qin Wu,et al.  Empirical correction to density functional theory for van der Waals interactions , 2002 .

[29]  Gustavo E. Scuseria,et al.  Linear Scaling Density Functional Calculations with Gaussian Orbitals , 1999 .

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

[31]  Jorge M. Seminario,et al.  Recent developments and applications of modern density functional theory , 1996 .

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