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Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional

Su, Julius T. and Xu, Xin and Goddard, William A., III (2004) Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional. Journal of Physical Chemistry A, 108 (47). pp. 10518-10526. ISSN 1089-5639. doi:10.1021/jp047502+.

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We predict structures and energies of water clusters containing up to 19 waters with X3LYP, an extended hybrid density functional designed to describe noncovalently bound systems as accurately as covalent systems. Our work establishes X3LYP as the most practical ab initio method today for calculating accurate water cluster structures and energies. We compare X3LYP/aug-cc-pVTZ energies to the most accurate theoretical values available (n = 2−6, 8), MP2 with basis set superposition error (BSSE) corrections extrapolated to the complete basis set limit. Our energies match these reference energies remarkably well, with a root-mean-square difference of 0.1 kcal/mol/water. X3LYP also has ten times less BSSE than MP2 with similar basis sets, allowing one to neglect BSSE at moderate basis sizes. The net result is that X3LYP is ∼100 times faster than canonical MP2 for moderately sized water clusters.

Item Type:Article
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URLURL TypeDescription Information
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2004 American Chemical Society. Received 9 June 2004. Published online 2 November 2004. Published in print 1 November 2004. This research was funded partially by NSF (CHE 9985574), by NIH (HD 36385-02), and by DOE-ASCI. The facilities of the Materials and Process Simulation Center used in these studies were funded by ARO-DURIP, ONR-DURIP, NSF-MRI, a SUR grant from IBM, and the Beckman Institute. In addition, the Materials and Process Simulation Center is funded by grants from ARO-MURI, ONR-MURI, ONR-DARPA, NIH, NSF, General Motors, ChevronTexaco, Seiko-Epson, and Asahi Kasei. We thank Mr. Christopher L. McClendon for initial suggestions and Prof. Jian Wan, Central China Normal University, for helping with some of the calculations.
Funding AgencyGrant Number
NSFCHE 9985574
NIHHD 36385-02
Department of Energy (DOE)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Issue or Number:47
Record Number:CaltechAUTHORS:20170524-144024380
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Official Citation:Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional Julius T. Su, Xin Xu, and William A. Goddard III The Journal of Physical Chemistry A 2004 108 (47), 10518-10526 DOI: 10.1021/jp047502+
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77728
Deposited By: Ruth Sustaita
Deposited On:24 May 2017 22:04
Last Modified:15 Nov 2021 17:33

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