Using optimally tuned range separated hybrid functionals in ground-state calculations: Consequences and caveats

被引:168
作者
Karolewski, Andreas [1 ]
Kronik, Leeor [2 ]
Kuemmel, Stephan [1 ]
机构
[1] Univ Bayreuth, D-95440 Bayreuth, Germany
[2] Weizmann Inst Sci, Dept Mat & Interfaces, IL-76100 Rehovot, Israel
基金
欧洲研究理事会;
关键词
GENERALIZED-GRADIENT-APPROXIMATION; CHARGE-TRANSFER EXCITATIONS; DENSITY FUNCTIONALS; ELECTRONS; ENERGY; FIELD;
D O I
10.1063/1.4807325
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
引用
收藏
页数:11
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