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Scientific article
English

How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?

Published inTheoretical Chemistry accounts, vol. 133, no. 1, 1405
Publication date2014
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.

Keywords
  • Frozen-density
  • Embedding theory
  • Linear-response
  • Time-dependent density functional
Research group
Citation (ISO format)
HUMBERT-DROZ, Marie et al. How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations? In: Theoretical Chemistry accounts, 2014, vol. 133, n° 1, p. 1405. doi: 10.1007/s00214-013-1405-1
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Article (Published version)
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ISSN of the journal1432-2234
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