Electronic Supporting Information
Electronic Supporting Information
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DOI：
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发表时间：
2016
影响因子：
4.8
通讯作者：
J. Mewes;J. Herbert;A. Dreuw
中科院分区：
文献类型：
--
作者：
J. Mewes;J. Herbert;A. Dreuw
Correlated groundand excited-state densities are required to compute the respective reaction fields. Formally, these densities can be obtained from the respective wavefunctions, which corresponds to unrelaxed densities, or by computing the energy-derivative with respect to an electric field, yielding relaxed densities. Within our implementation of ADC, excited-state densities are obtained via the intermediate-state representation (ISR) formalism consistent to the given order in perturbation theory. ADC is not a linear response method, and these densities are not “relaxed” in the aforementioned sense (i.e. they do not include an explicitly calculated orbital relaxation). They nevertheless contain significant density relaxation effects, as demonstrated recently at second order, provide an accurate description of vertical excitation energies in solution, and are inexpensive to compute. To compute the densities, the converged ADC excited-state vectors are combined with the intermediatestate basis of the appropriate order, yielding an excitedstate wave function. Eventually, the excited-state densities used for the PCM calculations are consistent to first order for ADC(1) and to second order for ADC(2). For the third order methods an efficient implementation of the ISR of corresponding order is not yet available. Therefore, the ISR of second order is used in combination with the third-order state vectors, which is the definition of the mixed ADC(3/2) approach, referred to as ADC(3) in the following. Accordingly, for all approaches involving a MP(3) ground state, the solute-solvent interaction is accounted for using MP(2) densities.
