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Generalized generalized gradient approximation: An improved density-functional theory for accurate orbital eigenvalues

Hua, Xinlei and Chen, Xiaojie and Goddard, W. A., III (1997) Generalized generalized gradient approximation: An improved density-functional theory for accurate orbital eigenvalues. Physical Review B, 55 (24). pp. 16103-16109. ISSN 0163-1829. http://resolver.caltech.edu/CaltechAUTHORS:HUAprb97

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Abstract

The generalized gradient approximation (GGA) for the exchange functional in conjunction with accurate expressions for the correlation functional have led to numerous applications in which density-functional theory (DFT) provides structures, bond energies, and reaction activation energies in excellent agreement with the most accurate ab initio calculations and with the experiment. However, the orbital energies that arise from the Kohn-Sham auxiliary equations of DFT may differ by a factor of 2 from the ionization potentials, indicating that excitation energies and properties involving sums over excited states (nonlinear-optical properties, van der Waals attraction) may be in serious error.mWe propose herein a generalization of the GGA in which the changes in the functionals due to virtual changes in the orbitals are allowed to differ from the functional used to map the exact density onto the exact energy. Using the simplest version of this generalized GGA we show that orbital energies are within ∼5% of the correct values and the long-range behavior has the correct form.


Item Type:Article
Additional Information:©1997 The American Physical Society. Received 13 January 1997. The research was funded by NSF (CHE 95-22179 and ASC 92-17368). The facilities of the MSC are also supported by grants from DOE-BCTR, Asahi Chemical, Chevron Petroleum Technology, Owens Corning, Saudi Aramco, Chevron Chemical Co., Asahi Glass, Nippon Steel, Hercules, BP Chemical, Avery Dennison, and Beckman Institute. Some of these calculations were carried out on the JPL Cray and the San Diego Supercomputer.
Subject Keywords:EXCHANGE; THERMOCHEMISTRY
Record Number:CaltechAUTHORS:HUAprb97
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:HUAprb97
Alternative URL:http://dx.doi.org/10.1103/PhysRevB.55.16103
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4177
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Aug 2006
Last Modified:26 Dec 2012 08:58

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