Jump to main content
Jump to site search

Issue 4, 2018
Previous Article Next Article

Approximate DFT-based methods for generating diabatic states and calculating electronic couplings: models of two and more states

Author affiliations

Abstract

Four types of density functional theory (DFT)-based approaches are assessed in this work for the approximate construction of diabatic states and the evaluation of electronic couplings between these states. These approaches include the constrained DFT (CDFT) method, the constrained noninteracting electron (CNE) model to post-process Kohn–Sham operators, the approximate block-diagonalization (BD) of the Kohn–Sham operators, and the generalized Mulliken–Hush method. It is shown that the first three approaches provide a good description for long-distance intermolecular electron transfer (ET) reactions. On the other hand, inconsistent results were found when applying these approaches to intramolecular ET in strongly coupled, mixed-valence systems. Model analysis shows that this discrepancy is caused by the inappropriate use of the two-state model rather than the defects of the approaches themselves. The situation is much improved when more states are included in the model electronic Hamiltonian. The CNE and BD approaches can thus serve as efficient and robust alternatives for building ET models based on DFT calculations.

Graphical abstract: Approximate DFT-based methods for generating diabatic states and calculating electronic couplings: models of two and more states

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Sep 2017, accepted on 18 Dec 2017 and first published on 20 Dec 2017


Article type: Paper
DOI: 10.1039/C7CP06660K
Citation: Phys. Chem. Chem. Phys., 2018,20, 2571-2584
  •   Request permissions

    Approximate DFT-based methods for generating diabatic states and calculating electronic couplings: models of two and more states

    C. Yang, C. Yam and H. Wang, Phys. Chem. Chem. Phys., 2018, 20, 2571
    DOI: 10.1039/C7CP06660K

Search articles by author

Spotlight

Advertisements