Journal
THEORETICAL CHEMISTRY ACCOUNTS
Volume 133, Issue 1, Pages -Publisher
SPRINGER
DOI: 10.1007/s00214-013-1405-1
Keywords
Frozen-Density Embedding Theory; Linear-response time-dependent density functional theory; Solvatochromism; Molecular clusters; Multi-level simulations
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Funding
- Swiss National Science Foundation [200020/134791/1 FNRS]
- COST (CODECS)
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According to Frozen-Density Embedding Theory, any observable evaluated for the embedded species is a functional of the frozen density (rho (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 rho (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 rho (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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