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

Literature Information

Publication Date 2017-12-20
DOI 10.1039/C7CP06660K
Impact Factor 3.676
Authors

ChiYung Yam


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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