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Polarizable Frozen Density Embedding with External Orthogonalization

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [2]
  1. Pennsylvania State Univ., University Park, PA (United States); The Pennsylvania State University
  2. Pennsylvania State Univ., University Park, PA (United States)
+ Show Author Affiliations
In this work, 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.
Research Organization:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018038
OSTI ID:
1843983
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 12 Vol. 15; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrical properties
Metal clusters
Molecules
Polarity
Pyridines