MURAL - Maynooth University Research Archive Library



    Time-Dependent Density Functional Theory as a Foundation for a Firmer Understanding of Sum-Over-States Density Functional Perturbation Theory: “Loc.3” Approximation


    Fadda, Elisa and Casida, Mark E. and Salahub, Dennis R. (2003) Time-Dependent Density Functional Theory as a Foundation for a Firmer Understanding of Sum-Over-States Density Functional Perturbation Theory: “Loc.3” Approximation. International Journal of Quantum Chemistry, 91 (2). pp. 67-83. ISSN 0020-7608

    [img]
    Preview
    Download (182kB) | Preview


    Share your research

    Twitter Facebook LinkedIn GooglePlus Email more...



    Add this article to your Mendeley library


    Abstract

    Sum-over-states density functional perturbation theory (SOS-DFPT) (Malkin, V. G.; Malkina, O. L.; Casida, M. E.; Salahub, D. R. J Am Chem Soc 1994, 116, 5898) has been successful as a method for calculating nuclear magnetic resonance (NMR) chemical shifts. The key to this success is the introduction of an ad hoc correction to the excitation energies represented by simple orbital energy differences in uncoupled density functional theory. It has been suggested (Jamorski, C.; Casida, M. E.; Salahub, D. R. J Chem Phys 1996, 104, 5134) that the good performance of this methodology could be partly explained by the resemblance of the corrected excitation energy to the orbital energy difference given by time-dependent density functional theory (TDDFT). In fact, according to exact (wave function) time-dependent perturbation theory, both magnetic and electric perturbations may be described using essentially the same simple SOS expression. However in adiabatic TDDFT, with no explicit relativistic or current density functional dependence, the functional is approximate and so the magnetic and electric SOS expressions are different. Because TDDFT (neglecting relativistic and current density functional dependence) is formally exact for electric perturbations but not magnetic perturbations and because the two SOS expressions should have the same form, we propose that the SOS expression for electric perturbations should also be used for magnetic perturbations. We then go on to realize our theory by deriving a “Loc.3” approximation that is explicitly designed by applying the electric field SOS expression to magnetic fields within the two-level model and Tamm–Dancoff approximation. Test results for 13 small organic and inorganic molecules show that the Loc.3 approximation performs at least as well as the “Loc.1” and “Loc.2” approximations of SOS-DFPT.

    Item Type: Article
    Keywords: sum-over-states density functional perturbation theory; NMR chemical shifts; time-dependent DFT; magnetic perturbations;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7831
    Identification Number: https://doi.org/10.1002/qua.10434
    Depositing User: Elisa Fadda
    Date Deposited: 30 Jan 2017 15:04
    Journal or Publication Title: International Journal of Quantum Chemistry
    Publisher: Wiley
    Refereed: Yes
    URI:

    Repository Staff Only(login required)

    View Item Item control page

    Downloads

    Downloads per month over past year