Solvent-Induced Frequency Shifts: Configuration Interaction Singles Combined with the Effective Fragment Potential Method

TitleSolvent-Induced Frequency Shifts: Configuration Interaction Singles Combined with the Effective Fragment Potential Method
Publication TypeJournal Article
Year of Publication2010
AuthorsArora P, Slipchenko LV, Webb SP, DeFusco A, Gordon MS
Journal TitleJournal of Physical Chemistry A
Date Published07/01
ISBN Number1089-5639
Accession NumberISI:000278981900002
Keywordsab-initio, AQUEOUS-SOLUTION, COUPLED-CLUSTER, dipole-moment derivatives, electronic-transition, excitation-energies, excited-states, hartree-fock calculations, molecular-dynamics, solvation dynamics

The simplest variational method for treating electronic excited states, configuration interaction with single excitations (CIS), has been interfaced with the effective fragment potential (EFP) method to provide an effective and computationally efficient approach for studying the qualitative effects of solvents on the electronic spectra of molecules. Three different approaches for interfacing a non-self-consistent field (SCF) excited-state quantum mechanics (QM) method and the EFP method are discussed. The most sophisticated and complex approach (termed fully self consistent) calculates the excited-state electron density with fully self-consistent accounting for the polarization (induction) energy of effective fragments. The simplest approach (method I) includes a strategy that indirectly adds the EFP perturbation to the CIS wave function and energy via modified Hartree-Fock molecular orbitals, so that there is no direct EFP interaction with the excited-state density. An intermediate approach (method 2) accomplishes the latter in a noniterative perturbative manner. Theoretical descriptions of the three approaches are presented, and test results of solvent-induced shifts using methods 1 and 2 are compared with fully ab initio values. These comparisons illustrate that, at least for the test cases examined here, modification of the ground-state Hartree-Fock orbitals is the largest and most important factor in the calculated solvent-induced shifts. Method 1 is then employed to study the aqueous solvation of coumarin 151 and compared with experimental measurements.

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