An extended hybrid density functional (X3LYP) with improved descriptions of van der Waals and hydrogen bonded interactions plus electronic and thermodynamic properties of molecular systems.

Journal Article · Wed Jun 01 04:00:00 EDT 2005 · Proposed for publication in the Journal of Chemical Physics.

OSTI ID:970742

Muller, Richard Partain ^[1]; Goddard, III, William A ^[1]; Zhang, Qingsong ^[1]; Xu, Xin ^[1]

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1. California Institute of Technology, Pasadena, CA

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.

• Research Organization: Sandia National Laboratories
• Sponsoring Organization: USDOE
• DOE Contract Number: AC04-94AL85000
• OSTI ID: 970742
• Report Number(s): SAND2005-3529J
• Journal Information: Proposed for publication in the Journal of Chemical Physics., Journal Name: Proposed for publication in the Journal of Chemical Physics.
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
ATOMS
DIMERS
ELECTRONS
ENERGY DENSITY
FUNCTIONALS
HYDROGEN
IONIZATION POTENTIAL
PROTONS
THERMODYNAMIC PROPERTIES
WATER