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J Chem Phys. 2013 May 28;138(20):204115. doi: 10.1063/1.4807325.

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

Author information

1
Theoretical Physics IV, University of Bayreuth, 95440 Bayreuth, Germany.

Abstract

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.

PMID:
23742462
DOI:
10.1063/1.4807325

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