Solvent effects on optical properties of molecules: A combined time-dependent density functional theory/effective fragment potential approach

Yoo, Soohaeng; Zahariev, Federico; Sok, Sarom; Gordon, Mark S.

doi:10.1063/1.2992049

Cited by 98 publications

(125 citation statements)

References 46 publications

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“…72 The averaged gas-phase and aqueousphase acetone n f π* vertical excitation energies and solventinduced shifts are compared in Table 5 with previous experimental measurements 70,71 and theoretical calculations. 30 The CIS/ EFP1 vertical excitation energies are overestimated, reflecting the approximate nature of the CIS method; however, the solventinduced shifts in the absorption spectrum predicted by CIS/ EFP1 are in qualitative agreement with the previous results.…”

Section: Resultssupporting

confidence: 79%

“…Yoo et al combined the TDDFT method for excited states with EFP to study the optical properties of molecules in the condensed phase. 30 This TDDFT/EFP investigation successfully reproduced the experimentally observed solvent-induced shifts of acetone. While the present work focuses on the simple CIS method, the strategies that are presented here are relevant for most ab initio excited-state methods.…”

Section: Introductionsupporting

confidence: 55%

“…Acetone in 100 EFP1. The absorption of acetone has been extensively studied in previous theoretical calculations 30,50,68,69 as well as in experimental measurements. [70][71][72] The S 0 to S 1 excitation in acetone is the n f π* excitation that occurs from an O lone pair into the π* orbital of the carbonyl double bond.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2010

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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 1) 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. PO Box 2206, Germantown, Maryland 20875 ReceiVed: February 27, 2010 ReVised Manuscript ReceiVed: May 20, 2010 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 1) 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 groun...

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Section: Resultssupporting

confidence: 79%

Section: Introductionsupporting

confidence: 55%

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

et al. 2010

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“…44 The solute is treated quantum mechanically using DFT and the PBE0 functional with the cc-pVDZ basis set. The solvent is treated using 100 EFP1/DFT solvent water molecules.…”

Section: Introductionmentioning

confidence: 99%

Solvent Induced Shifts in the UV Spectrum of Amides

2013

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Solvent effects on the electronic spectra of formamide and trans-N-methylacetamide are studied using four different levels of theory: singly excited configuration interaction (CIS), equations of motion coupled-cluster theory with singles and doubles (EOM-CCSD), completely renormalized coupled-cluster theory with singles and doubles with perturbative triple excitations (CR-EOM-CCSD(T)), and time-dependent density functional theory (TDDFT), employing small clusters of water molecules. The simulated electronic spectrum is obtained via molecular dynamics simulations with 100 waters modeled with the effective fragment potential method and exhibits a blue-shift and red-shift, respectively, for the n → π* and πnb → π* vertical excitation energies, in good agreement with the experimental electronic spectra of amides. Disciplines Chemistry CommentsReprinted (adapted) ABSTRACT: Solvent effects on the electronic spectra of formamide and trans-N-methylacetamide are studied using four different levels of theory: singly excited configuration interaction (CIS), equations of motion coupled-cluster theory with singles and doubles (EOM-CCSD), completely renormalized coupled-cluster theory with singles and doubles with perturbative triple excitations (CR-EOM-CCSD(T)), and time-dependent density functional theory (TDDFT), employing small clusters of water molecules. The simulated electronic spectrum is obtained via molecular dynamics simulations with 100 waters modeled with the effective fragment potential method and exhibits a blue-shift and red-shift, respectively, for the n → π* and π nb → π* vertical excitation energies, in good agreement with the experimental electronic spectra of amides.

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“…The effective fragment potential (EFP) method [58][59][60][61][62][63] provides a polarizable ab initio based solvent model to describe solute-solvent intermolecular interactions. The EFP method has been applied successfully to QM/MM studies of molecules in clusters and in solution.…”

Section: -2mentioning

confidence: 99%

Optimizing conical intersections of solvated molecules: The combined spin-flip density functional theory/effective fragment potential method

Minezawa

Gordon

2012

The Journal of Chemical Physics

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Solvent effects on a potential energy surface crossing are investigated by optimizing a conical intersection (CI) in solution. To this end, the analytic energy gradient has been derived and implemented for the collinear spinflip density functional theory (SFDFT) combined with the effective fragment potential (EFP) solvent model. The new method is applied to the azomethane-water cluster and the chromophore of green fluorescent protein in aqueous solution. These applications illustrate not only dramatic changes in the CI geometries but also strong stabilization of the CI in a polar solvent. Furthermore, the CI geometries obtained by the hybrid SFDFT/EFP scheme reproduce those by the full SFDFT, indicating that the SFDFT/EFP method is an efficient and promising approach for understanding nonadiabatic processes in solution. Solvent effects on a potential energy surface crossing are investigated by optimizing a conical intersection (CI) in solution. To this end, the analytic energy gradient has been derived and implemented for the collinear spin-flip density functional theory (SFDFT) combined with the effective fragment potential (EFP) solvent model. The new method is applied to the azomethane-water cluster and the chromophore of green fluorescent protein in aqueous solution. These applications illustrate not only dramatic changes in the CI geometries but also strong stabilization of the CI in a polar solvent. Furthermore, the CI geometries obtained by the hybrid SFDFT/EFP scheme reproduce those by the full SFDFT, indicating that the SFDFT/EFP method is an efficient and promising approach for understanding nonadiabatic processes in solution.

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Solvent effects on optical properties of molecules: A combined time-dependent density functional theory/effective fragment potential approach

Cited by 98 publications

References 46 publications

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

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

Solvent Induced Shifts in the UV Spectrum of Amides

Optimizing conical intersections of solvated molecules: The combined spin-flip density functional theory/effective fragment potential method

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