The determination of hyperpolarizabilities using density functional theory with nonlocal functionals

The theory for the coupled perturbed Kohn–Sham calculation of hyperpolarizabilities using nonlocal density functionals is presented. Results for calculations on formaldehyde, acetonitrile, and methyl fluoride using moderate size basis sets are reported. These results are compared with previous density functional calculations using the local density approximation, Hartree–Fock, and correlated methods, and with the experimental values.

[1]  David P. Shelton,et al.  A comparison of calculated and experimental hyperpolarizabilities for acetonitrile in gas and liquid phases , 1993 .

[2]  P. Fowler.  An SCF calculation of the derivatives of the multipole moments and polarizabilities of formaldehyde , 1982 .

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

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

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

[6]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules , 1971 .

[7]  Michael C. Zerner,et al.  The Challenge of d and f electrons : theory and computation , 1989 .

[8]  N. Handy,et al.  The determination of hyperpolarisabilities using density functional theory , 1993 .

[9]  N. Handy,et al.  Frequency dependent hyperpolarizabilities with application to formaldehyde and methyl fluoride , 1990 .

[10]  T. H. Dunning.  Gaussian Basis Functions for Use in Molecular Calculations. III. Contraction of (10s6p) Atomic Basis Sets for the First‐Row Atoms , 1970 .

[11]  Nicholas C. Handy,et al.  Kohn—Sham bond lengths and frequencies calculated with accurate quadrature and large basis sets , 1992 .

[12]  M. Spackman.  Accurate prediction of static dipole polarizabilities with moderately sized basis sets , 1989 .

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

[14]  N. Handy,et al.  The determination of magnetisabilities using density functional theory , 1994 .