期刊
JOURNAL OF CHEMICAL PHYSICS
卷 138, 期 20, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4807325
关键词
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资金
- German-Israeli Foundation
- DFG [GRK 1640]
- European Research Council
- Lise Meitner Minerva Center for Computational Chemistry
Optimally tuned range separated hybrid functionals are a new class of implicitly defined functionals. Their important new aspect is that the range separation parameter in these functionals is determined individually for each system by iteratively tuning it until a fundamental, non-empirical condition is fulfilled. Such functionals have been demonstrated to be extremely successful in predicting electronic excitations. In this paper, we explore the use of the tuning approach for predicting ground state properties. This sheds light on one of its downsides - the violation of size consistency. By analyzing diatomic molecules, we reveal size consistency errors up to several electron volts and find that binding energies cannot be predicted reliably. Further consequences of the consistent ground-state use of the tuning approach are potential energy surfaces that are qualitatively in error and an incorrect prediction of spin states. We discuss these failures, their origins, and possibilities for overcoming them. (C) 2013 AIP Publishing LLC.
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