Application of spin-restricted open-shell Kohn-Sham method to atomic and molecular multiplet states

A recently proposed spin-restricted open-shell Kohn–Sham (ROKS) method is applied to investigate various atomic and molecular multiplet states. A wide range of multiplets is considered: multiplet terms for which the spin-restricted open-shell theory of Roothaan applies, as well as state situations which cannot be described by Roothaan’s theory (e.g., states of square cyclobutadiene, etc.). Problems associated with the use of approximate density functionals and possible perspectives of the ROKS method are discussed.

[1]  Dennis R. Salahub,et al.  Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold , 1998 .

[2]  S. Shaik,et al.  Spin-restricted density functional approach to the open-shell problem , 1998 .

[3]  Ágnes Nagy.  Kohn-Sham equations for multiplets , 1998 .

[4]  A. Theophilou.  Rigorous formulation of a Kohn and Sham theory for states with special symmetries , 1998 .

[5]  S. Trickey,et al.  Fukutome symmetry classification of the Kohn–Sham auxiliary one‐matrix and its associated state or ensemble , 1998 .

[6]  E. Baerends,et al.  Exchange and correlation energy in density functional theory. Comparison of accurate DFT quantities with traditional Hartree-Fock based ones and generalized gradient approximations for the molecules Li2, N2, F2. , 1997 .

[7]  Walter Thiel,et al.  A new gradient-corrected exchange-correlation density functional , 1997 .

[8]  Claude Daul,et al.  DENSITY FUNCTIONAL CALCULATIONS OF OPTICAL EXCITATION ENERGIES BY A TRANSITION-STATE METHOD , 1997 .

[9]  A. Savin,et al.  A correlation-energy density functional for multideterminantal wavefunctions , 1997 .

[10]  S. Peyerimhoff,et al.  Radiationless Transitions between the First Excited Triplet State and the Singlet Ground State in Ethylene: A Theoretical Study , 1996 .

[11]  Stefan Grimme,et al.  Density functional calculations with configuration interaction for the excited states of molecules , 1996 .

[12]  Nicholas C. Handy,et al.  Exchange functionals and potentials , 1996 .

[13]  A. Becke,et al.  Extension of the local-spin-density exchange-correlation approximation to multiplet states , 1995 .

[14]  Rodney J. Bartlett,et al.  A multireference coupled‐cluster study of the ground state and lowest excited states of cyclobutadiene , 1994 .

[15]  C. Daul.  DENSITY FUNCTIONAL THEORY APPLIED TO THE EXCITED STATES OF COORDINATION COMPOUNDS , 1994 .

[16]  Görling.  Symmetry in density-functional theory. , 1993, Physical review. A, Atomic, molecular, and optical physics.

[17]  M. Platz.  Kinetics and spectroscopy of carbenes and biradicals , 1990 .

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

[19]  Oliveira,et al.  Density-functional theory for ensembles of fractionally occupied states. I. Basic formalism. , 1988, Physical review. A, General physics.

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

[21]  A. Voter,et al.  The generalized resonating valence bond description of cyclobutadiene , 1986 .

[22]  Warren J. Hehre,et al.  AB INITIO Molecular Orbital Theory , 1986 .

[23]  Elliott H. Lieb,et al.  Density Functionals for Coulomb Systems , 1983 .

[24]  H. Englisch,et al.  Hohenberg-Kohn theorem and non-V-representable densities , 1983 .

[25]  Mel Levy,et al.  Electron densities in search of Hamiltonians , 1982 .

[26]  S. Peyerimhoff,et al.  Theoretical prediction of the potential curves for the lowest‐lying states of the CSi+ and Si2+ molecular ions , 1981 .

[27]  E. Davidson,et al.  Theoretical studies of diradicals containing four .pi. electrons , 1981 .

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

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

[30]  J. Wood.  Atomic multiplet structures obtained from Hartree-Fock, statistical exchange and local spin density approximations , 1980 .

[31]  U. V. Barth,et al.  Local-density theory of multiplet structure , 1979 .

[32]  Arvi Rauk,et al.  On the calculation of multiplet energies by the hartree-fock-slater method , 1977 .

[33]  B. Lundqvist,et al.  Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism , 1976 .

[34]  W. T. Borden.  Can a square or effectively square singlet be the ground state of cyclobutadiene , 1975 .

[35]  B. I. Bennett,et al.  Singlet–triplet splittings as obtained from the Xα-scattered wave method: A theoretical analysis , 1975 .

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

[37]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[38]  C. C. J. Roothaan,et al.  Self-Consistent Field Theory for Open Shells of Electronic Systems , 1960 .

[39]  B. Rabinovitch,et al.  Kinetics of the Thermal Cis‐Trans Isomerization of Dideuteroethylene , 1955 .