Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction

Xinxin Cheng, Yao Zhang, Elvar Jónsson, Hannes Jónsson and Peter M. Weber ()
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Xinxin Cheng: Brown University, 324 Brook Street
Yao Zhang: Brown University, 324 Brook Street
Elvar Jónsson: COMP, Aalto University
Hannes Jónsson: Brown University, 324 Brook Street
Peter M. Weber: Brown University, 324 Brook Street

Nature Communications, 2016, vol. 7, issue 1, 1-6

Abstract: Abstract Density functional theory (DFT) is widely applied in calculations of molecules and materials. Yet, it suffers from a well-known over-emphasis on charge delocalization arising from self-interaction error that destabilizes localized states. Here, using the symmetric diamine N,N′-dimethylpiperazine as a model, we have experimentally determined the relative energy of a state with positive charge localized on one of the two nitrogen atoms, and a state with positive charge delocalized over both nitrogen atoms. The charge-localized state was found to be 0.33 (0.04) eV higher in energy than the charge-delocalized state. This provides an important test of theoretical approaches to electronic structure calculations. Calculations with all DFT functionals commonly used today, including hybrid functionals with exact exchange, fail to predict a stable charge-localized state. However, the application of an explicit self-interaction correction to a semi-local functional identifies both states and gives relative energy in excellent agreement with both experiment and CCSD(T) calculations.

Date: 2016
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DOI: 10.1038/ncomms11013

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