Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 8, Issue 17, Pages 4314-4318Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.7b02023
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Funding
- National Science Foundation [DMR-1505343]
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Density functional theory (DFT) uses a density functional approximation (DFA) to add electron correlation to mean-field electronic structure calculations. Standard strategies (generalized gradient approximations GGAs, meta-GGAs, hybrids, etc.) for building DFAs, no matter whether based on exact constraints or empirical parametrization, all face a zero-sum game between overdelocalization (fractional charge error, FC) and underestimation of covalent bonding (fractional spin error, FS). This work presents an alternative strategy. Practical Rung 3.5 ingredients are used to implement insights from hyper-GGA DFAs that reduce both FS and FC errors. Prototypes of this strategy qualitatively improve FS and FC error over 40 years of standard DFAs while maintaining low cost and practical evaluation of properties. Numerical results ranging from transition metal thermochemistry to absorbance peaks and excited-state geometry optimizations highlight this strategy's promise and indicate areas requiring further development.
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