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Local-Field Effects in Linear Response Properties within a Polarizable Frozen Density Embedding Method

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 present a polarizable frozen density embedding (FDE) method for calculating polarizabilities of coupled subsystems. The method (FDE-pol) combines a FDE method with an explicit polarization model such that the expensive freeze/thaw cycles can be bypassed, and approximate nonadditive kinetic potentials are avoided by enforcing external orthogonality between the subsystems. To describe the polarization of the frozen environment, we introduce a Hirshfeld partition-based density-dependent method for calculating the atomic polarizabilities of atoms in molecules, which alleviates the need to fit the atomic parameters to a specific system of interest or to a larger general set of molecules. Further, we show that the Hirshfeld partition-based method predicts molecular polarizabilities close to the basis set limit, and thus, a single basis set-dependent scaling parameter can be introduced to improve the agreement against the reference polarizability data. To test the model, we characterized the uncoupled and coupled response of small interacting molecular complexes. Here, the coupled response properties include the perturbation of the frozen system due to the external perturbation which is ignored in the uncoupled response. We show that FDE-pol can accurately reproduce both the exact uncoupled polarizability and the coupled polarizabilities of the supermolecular systems. Using damped response theory, we also demonstrate that the coupled frequency-dependent polarizability can be described by including local field effects. The results emphasize the necessity of including local-field effects for describing the response properties of coupled subsystems, as well as the importance of accurate atomic polarizability models.
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:
1843984
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 1 Vol. 18; 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
Basis sets
Embedding
Molecules
Polarizability
Polarization