期刊
JOURNAL OF CHEMICAL PHYSICS
卷 143, 期 23, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4938103
关键词
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资金
- National Science Foundation Graduate Research Fellowship
- National Science Foundation [CHE-1464804]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1464804] Funding Source: National Science Foundation
Constrained density functional theory with configuration interaction (CDFT-CI) is a useful, low-cost tool for the computational prediction of electronic couplings between pseudo-diabatic constrained electronic states. Such couplings are of paramount importance in electron transfer theory and transition state theory, among other areas of chemistry. Unfortunately, CDFT-CI occasionally fails significantly, predicting a coupling that does not decay exponentially with distance and/or overestimating the expected coupling by an order of magnitude or more. In this communication, we show that the eigenvalues of the difference density matrix between the two constrained states can be used as an a priori metric to determine when CDFT-CI are likely to be reliable: when the eigenvalues are near 0 or +/- 1, transfer of a whole electron is occurring, and CDFT-CI can be trusted. We demonstrate the utility of this metric with several illustrative examples. (C) 2015 AIP Publishing LLC.
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