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

Published in Theoretical Chemistry Accounts. 2014, vol. 133, no. 1, p. 1405
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-densityEmbedding theoryLinear-responseTime-dependent density functional
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Other version: http://link.springer.com/10.1007/s00214-013-1405-1
Research group Groupe Wezolowski
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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. https://archive-ouverte.unige.ch/unige:33263

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Deposited on : 2014-01-15

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