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The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems

Xu, Xin and Goddard, William A., III (2004) The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems. Journal of Chemical Physics, 121 (9). pp. 4068-4082. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:XUXjcp04

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Abstract

Density functional theory (DFT) has become the method of choice for many applications of quantum mechanics to the study of the electronic properties of molecules and solids. Despite the enormous progress in improving the functionals, the current generation is inadequate for many important applications. As part of the quest of finding better functionals, we consider in this paper the Perdew-Burke-Ernzerhof (PBE) functional, which we believe to have the best theoretical foundation, but which leads to unacceptable errors in predicting thermochemical data (heats of formation) of molecular systems [mean absolute deviation (MAD)=16.9 kcal/mol against the extended G2 data set of 148 molecules]. Much improved thermochemistry is obtained with hybrid DFT methods that include part of the Hartree-Fock exchange [thus B3LYP (Becke's three parameter scheme combining Hartree-Fock exchange, Becke gradient corrected exchange functional and Lee-Yang-Parr correlational functional) with MAD=3.1 kcal/mol and PBE0 (Perdew's hybrid scheme using PBE exchange and correlation functionals) with MAD=4.8 kcal/mol]. However we wish to continue the quest for a pure density-based DFT. Thus we optimized the four free parameters (µ, kappa, alpha, and beta) in PBE theory against experimental atomic data and the van der Waals interaction properties of Ne2, leading to the xPBE extended functional, which significantly outperforms PBE for thermochemical properties MAD reduced to 8.0 kcal/mol while being competitive or better than PBE for predictions of geometric parameters, ionization potentials, electron affinities, and proton affinities and for the description of van der Waals and hydrogen bond interactions. Thus xPBE significantly enlarges the field of applications available for pure DFT. The functional forms thus obtained for the exchange and correlational functionals may be useful for discovering new improved functionals or formalisms.


Item Type:Article
Additional Information:©2004 American Institute of Physics. (Received 8 July 2003; accepted 18 May 2004) We thank Dr. Y. X. Cao, Dr. Dale Braden, and Dr. Jason Perry at Schrödinger Inc. for technical support in using and modifying Jaguar. This research was initiated with funding from National Institutes of Health (Grant No. HD 36385-02) and U.S. DOE (Grant No. ASCI-ASAP) and completed with funding from NSF (CHE and NIRT) and ONR. The facilities of the Materials and Process Simulation Center used in these studies were funded by ONR-DURIP, ARO-DURIP, NSFMRI, IBM-SUR, and the Beckman Institute. In addition, the Materials and Process Simulation Center is funded by grants from DOE-FETL, ARO-MURI, ONR-MURI, NIH, NSF, General Motors, ChevronTexaco, Seiko-Epson, Berlex Pharma, and Asahi Kasei. X.X. is also funded by the National Natural Science Foundation of China (Grant No. 20021002), National Natural Science Foundation of Fujian (Grant No. 2002F010), the Ministry of Science and Technology of China (Grant No. 2001CB610506), and TRAPOYT from the Ministry of Education of China.
Subject Keywords:thermodynamic properties; density functional theory; quantum theory; thermochemistry; heat of formation; HF calculations; optimisation; neon; ionisation potential; electron affinity; proton affinity; hydrogen bonds
Record Number:CaltechAUTHORS:XUXjcp04
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:XUXjcp04
Alternative URL:http://dx.doi.org/10.1063/1.1771632
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:2812
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:28 Apr 2006
Last Modified:26 Dec 2012 08:51

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