Quantum mechanical embedding theory based on a unique embedding potential

Chen Huang, Michele Pavone, Emily A. Carter

Research output: Contribution to journalArticlepeer-review

157 Scopus citations

Abstract

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 4σ and 5σ 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.

Original languageEnglish (US)
Article number154110
JournalJournal of Chemical Physics
Volume134
Issue number15
DOIs
StatePublished - Apr 21 2011

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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