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Published January 1, 2005 | Published
Journal Article Open

An extended hybrid density functional (X3LYP) with improved descriptions of nonbond interactions and thermodynamic properties of molecular systems


We derive here the form for the exact exchange energy density for a density that decays with Gaussian-type behavior at long range. This functional is intermediate between the B88 and the PW91 exchange functionals. Using this modified functional to match the form expected for Gaussian densities, we propose the X3LYP extended functional. We find that X3LYP significantly outperforms Becke three parameter Lee–Yang–Parr (B3LYP) for describing van der Waals and hydrogen bond interactions, while performing slightly better than B3LYP for predicting heats of formation, ionization potentials, electron affinities, proton affinities, and total atomic energies as validated with the extended G2 set of atoms and molecules. Thus X3LYP greatly enlarges the field of applications for density functional theory. In particular the success of X3LYP in describing the water dimer (with Re and De within the error bars of the most accurate determinations) makes it an excellent candidate for predicting accurate ligand–protein and ligand–DNA interactions.

Additional Information

© 2005 American Institute of Physics. (Received 15 June 2004; accepted 10 September 2004; published online 13 December 2004) We thank Dr. Y. X. Cao, Dr. Dale Braden, and Dr. Jason Perry at Schrödinger Inc. for technical support of using and programming with Jaguar. This research was funded by DOE (ASCI), DARPA-CMDF, DARPA-PROM, National Institutes of Health (HD 36385-02), National Natural Science Foundation of China (20021002), National Natural Science Foundation of Fujian (2002F010), the Ministry of Science and Technology of China (2001CB610506) and TRAPOYT from the Ministry of Education of China. The facilities of the Materials and Process Simulation Center (MSC) used in these studies were funded by DURIP-ARO, DURIP-ONR, IBM (SUR), NSF (MRI), and the Beckman Institute. In addition, the MSC is funded by grants from DOE-FETL, AROMURI, ONR-MURI, NIH, ChevronTexaco, Aventis Pharma, General Motors, Seiko-Epson, Berlex Biopharma, and Asahi Kasei.

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