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Bonding Properties of the Water Dimer: A Comparative Study of Density Functional Theories

Xu, Xin and Goddard, William A., III (2004) Bonding Properties of the Water Dimer: A Comparative Study of Density Functional Theories. Journal of Physical Chemistry A, 108 (12). pp. 2305-2313. ISSN 1089-5639. doi:10.1021/jp035869t.

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For a variety of density functional theories, we examined the ground-state properties of the water monomer (geometry, vibrational frequencies, dipole moment, polarizability) and dimer (geometry, vibrational frequencies, bond energy, and barrier heights for the transition states for the interchange of hydrogen atoms within the dimer). Thus, we considered LDA (SVWN), seven pure GGA methods (BLYP, BP86, BPW91, PWPW, mPWPW, PBEPBE, and XLYP), and eight hybrid GGA methods (BH&HLYP, B3LYP, B3P86, B3PW91, PW1PW, mPW1PW, PBE1PBE and X3LYP). We find that the best overall performance is given by X3LYP, a hybrid method using a modified GGA constructed from a linear combination of the Becke and Perdew GGAs. Comparing with the exact values, the errors in X3LYP for the water dimer are 0.05 kcal/mol (bond energy), 0.004 Å (bond distance), and 12 cm^(-1) (vibrational modes), and for the monomer, the errors are 0.002 Å (bond distance), 0.6° (bond angle), 14 cm^(-1) (vibrational modes), 0.005 D (dipole moment), and 0.008 Å^3 (polarizability). These data were not used in determining the parameters or form of X3LYP, suggesting that X3LYP should be generally useful for predicting accurate properties for systems dominated by hydrogen bonding, electrostatics, and van der Waals (dispersion) interactions, such as ligand/protein complexes.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2004 American Chemical Society. Received: June 30, 2003; In Final Form: December 9, 2003. Publication Date (Web): March 2, 2004. This research was funded partially by NSF (CHE 9985574) and by NIH (HD 36385-02). 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 DOE-ASCI, ARO-MURI, ONR-MURI, ONR-DARPA, NIH, NSF, General Motors, ChevronTexaco, Seiko-Epson, and Asahi Kasei.
Funding AgencyGrant Number
NSFCHE 9985574
NIHHD 36385-02
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20170524-084008185
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Official Citation:Bonding Properties of the Water Dimer:  A Comparative Study of Density Functional Theories Xin Xu and William A. Goddard, III The Journal of Physical Chemistry A 2004 108 (12), 2305-2313 DOI: 10.1021/jp035869t
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77695
Deposited By: Tony Diaz
Deposited On:24 May 2017 17:06
Last Modified:15 Nov 2021 17:33

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