Quantum mechanical embedding theory based on a unique embedding potential

Journal Article · Thu Apr 21 00:00:00 EDT 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3577516· OSTI ID:21560156

Huang, Chen ^[1]; Pavone, Michele; Carter, Emily A ^[2]

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1. Department of Physics, Princeton University, Princeton, New Jersey 08544 (United States)
2. Department of Mechanical and Aerospace Engineering, Program in Applied and Computational Mathematics, and the Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544-5263 (United States)

We remove the nonuniqueness of the embedding potential that exists in most previous quantum mechanical embedding schemes by letting the environment and embedded region share a common embedding (interaction) potential. To efficiently solve for the embedding potential, an optimized effective potential method is derived. This embedding potential, which eschews use of approximate kinetic energy density functionals, is then used to describe the environment while a correlated wavefunction (CW) treatment of the embedded region is employed. We first demonstrate the accuracy of this new embedded CW (ECW) method by calculating the van der Waals binding energy curve between a hydrogen molecule and a hydrogen chain. We then examine the prototypical adsorption of CO on a metal surface, here the Cu(111) surface. In addition to obtaining proper site ordering (top site most stable) and binding energies within this theory, the ECW exhibits dramatic changes in the p-character of the CO 4{sigma} and 5{sigma} orbitals upon adsorption that agree very well with x-ray emission spectra, providing further validation of the theory. Finally, we generalize our embedding theory to spin-polarized quantum systems and discuss the connection between our theory and partition density functional theory.

• OSTI ID: 21560156
• Journal Information: Journal of Chemical Physics, Vol. 134, Issue 15; Other Information: DOI: 10.1063/1.3577516; (c) 2011 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACCURACY
ADSORPTION
APPROXIMATIONS
BINDING ENERGY
CARBON MONOXIDE
DENSITY
DENSITY FUNCTIONAL METHOD
EMISSION SPECTRA
HYDROGEN
INTERACTIONS
KINETIC ENERGY
MOLECULES
PARTITION
POTENTIALS
QUANTUM MECHANICS
SPIN ORIENTATION
SURFACES
VAN DER WAALS FORCES
WAVE FUNCTIONS
X-RAY SPECTRA
CALCULATION METHODS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
ELEMENTS
ENERGY
FUNCTIONS
MECHANICS
NONMETALS
ORIENTATION
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
SORPTION
SPECTRA
VARIATIONAL METHODS