How to choose the frozen density in frozen-density embedding theory-based numerical simulations of local excitations?

Humbert-Droz, Marie, Zhou, Xiuwen, Shedge, Sapana V. and Wesolowski, Tomasz A. (2014) How to choose the frozen density in frozen-density embedding theory-based numerical simulations of local excitations?. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 133 . doi:10.1007/s00214-013-1405-1


Author Humbert-Droz, Marie
Zhou, Xiuwen
Shedge, Sapana V.
Wesolowski, Tomasz A.
Title How to choose the frozen density in frozen-density embedding theory-based numerical simulations of local excitations?
Journal name Theoretical Chemistry Accounts: Theory, Computation, and Modeling   Check publisher's open access policy
ISSN 1432-881X
1432-2234
Publication date 2014-01-01
Year available 2013
Sub-type Article (original research)
DOI 10.1007/s00214-013-1405-1
Open Access Status Not yet assessed
Volume 133
Total pages 20
Place of publication Heidelberg, Germany
Publisher Springer
Language eng
Formatted abstract
According to Frozen-Density Embedding Theory, any observable evaluated for the embedded species is a functional of the frozen density (ρB-the density associated with the environment). The environment-induced shifts in the energies of local excitations in organic chromophores embedded in hydrogen-bonded environments are analyzed. The excitation energies obtained for ρB, which is derived from ground-state calculations for the whole environment applying medium quality basis sets (STO- DZP) or larger, vary in a narrow range (about 0.02 eV which is at least one order of magnitude less than the magnitude of the shift). At the same time, the ground-state dipole moment of the environment varies significantly. The lack of correlation between the calculated shift and the dipole moment of the environment reflects the fact that, in Frozen-Density Embedding Theory, the partitioning of the total density is not unique. As a consequence, such concepts as "environment polarization" are not well defined within Frozen-Density Embedding Theory. Other strategies to generate ρB (superposition of densities of atoms/molecules in the environment) are shown to be less robust for simulating excitation energy shifts for chromophores in environments comprising hydrogen-bonded molecules.
Keyword Frozen-density embedding theory
Linear-response time-dependent density functional theory
Molecular clusters
Multi-level simulations
Solvatochromism
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Mathematics and Physics
 
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