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

Xinxin Cheng, Yao Zhang, Elvar Jónsson, Hannes Jónsson, Peter M. Weber*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

26 Citations (Scopus)
136 Downloads (Pure)

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.

Original languageEnglish
Article number11013
Pages (from-to)1-6
JournalNature Communications
Volume7
DOIs
Publication statusPublished - 16 Mar 2016
MoE publication typeA1 Journal article-refereed

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