TITLE

Molecular-orbital-free algorithm for the excited-state force in time-dependent density functional theory

AUTHOR(S)
Liu, Jie; Liang, Wan Zhen
PUB. DATE
January 2011
SOURCE
Journal of Chemical Physics;1/28/2011, Vol. 134 Issue 4, p044114
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Starting from the equation of motion in the density matrix formulation, we reformulate the analytical gradient of the excited-state energy at the time-dependent density functional theory level in the nonorthogonal Gaussian atom-centered orbital (AO) basis. Analogous to the analytical first derivative in molecular-orbital (MO) basis, a Z-vector equation has been derived with respect to the reduced one-electronic density matrix in AO basis, which provides a potential possibility to exploit quantum locality of the density matrix and avoids the matrix transformation between the AO and the MO basis. Numerical tests are finished for the excited-state geometry optimization and adiabatic excitation energy calculation of a series of small molecules. The results demonstrate the computational efficiency and accuracy of the current AO-based energy gradient expression in comparison with the MO-based scheme.
ACCESSION #
57679533

 

Related Articles

  • The role of orbital transformations in coupled-pair functionals. Kollmar, Christian; Heßelmann, Andreas // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Nov2010, Vol. 127 Issue 4, p311 

    The replacement of single excitations by orbital transformations in coupled-pair functionals derived from a single double configuration interaction approach is discussed. It is demonstrated that this modification leads to considerably improved density matrices and better agreement with results...

  • Communications: Accurate description of atoms and molecules by natural orbital functional theory. Piris, M.; Matxain, J. M.; Lopez, X.; Ugalde, J. M. // Journal of Chemical Physics;1/21/2010, Vol. 132 Issue 3, p031103 

    The spin-conserving density matrix functional theory is used to propose an improved natural orbital functional. The Piris reconstruction functional, PNOF, which is based on an explicit form of the two-particle cumulant λ(Δ,Λ) satisfying necessary positivity conditions for the...

  • On the calculation of charge transfer transitions with standard density functionals using constrained variational density functional theory. Ziegler, Tom; Krykunov, Mykhaylo // Journal of Chemical Physics;8/21/2010, Vol. 133 Issue 7, p074104 

    It is well known that time-dependent density functional theory (TD-DFT) based on standard gradient corrected functionals affords both a quantitative and qualitative incorrect picture of charge transfer transitions between two spatially separated regions. It is shown here that the well known...

  • Bonding analysis for sterically uncongested simple aurocarbons CnAum1. Zaleski-Ejgierd, Patryk; Pyykkö, Pekka // Canadian Journal of Chemistry;Jul2009, Vol. 87 Issue 7, p798 

    The title series of simple model aurocarbons, CAu4, C2Au2, C2Au4, C2Au6, and C6Au6, is investigated using density functional theory with TPSS and B3LYP functionals and the second-order Møller–Plesset perturbation theory, with the latest Karlsruhe basis sets. The vibrational frequencies...

  • Poisson-transformed density fitting in relativistic four-component Dirac–Kohn–Sham theory. Belpassi, Leonardo; Tarantelli, Francesco; Sgamellotti, Antonio; Quiney, Harry M. // Journal of Chemical Physics;3/28/2008, Vol. 128 Issue 12, p124108 

    We present recent developments in the implementation of the density fitting approach for the Coulomb interaction within the four-component formulation of relativistic density functional theory [Belpassi et al., J. Chem. Phys. 124, 124104 (2006)]. In particular, we make use of the Poisson...

  • Modeling temporary anions in density functional theory: Calculation of the Fukui function. Tozer, David J.; De Proft, Frank // Journal of Chemical Physics;7/21/2007, Vol. 127 Issue 3, p034108 

    Two approaches are investigated for modeling electron densities of temporary anions in density functional theory (DFT). Both rely on an artificial binding of the excess electron, in one case by a compact basis set and in the other by a potential wall. The key feature of the calculations is that...

  • Theoretical investigation of molecular excited states in polar organic monolayers via an efficient embedding approach. Terentjevs, Aleksandrs; Fabiano, Eduardo; Della Sala, Fabio // Theoretical Chemistry Accounts: Theory, Computation, & Modeling;Mar2012, Vol. 131 Issue 3, p1 

    In this work, we present a theoretical investigation on excitation energies of organic molecules embedded in a periodic monolayer. We use the self-consistent periodic-image-charges embedding approach, which takes into account all the electrostatic effects, to compute the perturbation on...

  • A crystalline orbital study of polydiacetylenes. Tobita, Motoi; Hirata, So; Bartlett, Rodney J. // Journal of Chemical Physics;5/22/2001, Vol. 114 Issue 20 

    The electronic and structural properties of the ground and excited states of infinite polydiacetylene chains in acetylenic (PDA) and butatrienic (PBT) structures are studied by a series of ab initio crystalline orbital and linear-combination-of-atomic-orbital periodic density functional theory...

  • Jacob’s ladder of density functional approximations for the exchange-correlation energy. Perdew, John P.; Schmidt, Karla // AIP Conference Proceedings;2001, Vol. 577 Issue 1, p1 

    The ground-state energy and density of a many-electron system are often calculated by Kohn-Sham density functional theory. We describe a ladder of approximations for the exchange-correlation energy as a functional of the electron density. At the lowest rung of this ladder, the contribution to...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics