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

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Abstract

According to Frozen-Density Embedding Theory, any observable evaluated for the embedded species is a functional of the frozen density (ρ B —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 ρ B , 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 ρ B (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.

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Notes

  1. In the present work any reference to Density Functional Theory (DFT), subsystem DFT, Kohn–Sham DFT, and Frozen-Density Embedding Theory (FDET), concerns the exact formalisms and not approximate methods based on such formalisms.

  2. In the case of embedded interacting wavefunction of the truncated Configuration Interaction form, an additional term in the embedding potential is needed [22] but it is a matter of convention whether this term is considered a part of the embedding potential or the potential for subsystem A (see also the relevant discussion in Ref. [52]).

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Acknowledgments

Grants from Swiss National Science Foundation (200020/134791/1 FNRS) and COST (CODECS) are greatly appreciated.

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Authors and Affiliations

  1. Département de Chimie Physique, Université de Genève, 30, quai Ernest-Ansermet, 1211, Geneva 4, Switzerland

    Marie Humbert-Droz, Xiuwen Zhou, Sapana V. Shedge & Tomasz A. Wesolowski

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  1. Marie Humbert-Droz
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  2. Xiuwen Zhou
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  4. Tomasz A. Wesolowski
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Correspondence to Tomasz A. Wesolowski.

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Humbert-Droz, M., Zhou, X., Shedge, S.V. et al. How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?. Theor Chem Acc 133, 1405 (2014). https://doi.org/10.1007/s00214-013-1405-1

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