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Other version: http://link.springer.com/10.1007/s00214-013-1405-1
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, 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-density — Embedding theory — Linear-response — Time-dependent density functional|
|Research group||Groupe Wezolowski|
|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 https://archive-ouverte.unige.ch/unige:33263|