Polarizable Frozen Density Embedding with External Orthogonalization

Partha Pratim Pal, Pengchong Liu, Lasse Jensen

Research output: Contribution to journalArticle

Abstract

We report a polarizable subsystem density functional theory to describe electronic properties of molecules embedded on a metal cluster. Interaction between the molecule and metal cluster is described using frozen density embedding (FDE). Substituting the nonadditive kinetic potential (NAKP) by approximate functionals is circumvented by enforcing external orthogonality (EO) through a projection operator. The computationally expensive freeze/thaw (FT) cycles are bypassed by including a polarization term in the embedding operator. Furthermore, the combination of polarization and EO permits supermolecular basis set calculations, which was not possible for strongly interacting systems with existing kinetic energy functionals. To test the method, we described the ground state density of pyridine, water, and benzene on a silver cluster. Performing FT on top of EO results in exact density embedding for this category of systems and is thus used for benchmarking the method. We find that the density is reproduced to within 0.15e, and the dipole and quadrupole moments are within 18% of the reference points for subsystem separations ranging from bonding to noninteracting distances. Additionally, our formalism allows the flexibility of incorporating different density functionals to the molecular and the metallic subsystems reducing the overall computational cost.

Original languageEnglish (US)
Pages (from-to)6588-6596
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume15
Issue number12
DOIs
StatePublished - Dec 10 2019

    Fingerprint

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this