Nonexponential solvation dynamics of simple liquids and mixtures

Jarzȩba, Włodzimierz; Walker, Gilbert C.; Johnson, Alan W.; Barbara, Paul F.

doi:10.1016/0301-0104(91)80034-f

Cited by 205 publications

(196 citation statements)

References 37 publications

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“…Of course, as already mentioned, methanol is a "non-Debye" solvent, exhibiting at least one additional higher-frequency relaxation in the dielectricloss spectrum [49]. This is apparently manifested as a rapid solvation relaxation component (rs -I ps) in ultrafast TDFS measurements reported by Barbara et al in methanol [16,50]. The high-frequency component observed in the present simulations in methanol, r. -0.1 ps, is clearly much faster, occurring on a timescale below that readily accessible to TDFS experiments, and is not associated directly with the "non-Debye" properties of the pure methanol solvent.…”

Section: Implications For Et Solvent Dynamicsmentioning

confidence: 95%

Solvent dynamical effects in electron transfer: molecular dynamics simulations of reactions in methanol

1993

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Section: Implications For Et Solvent Dynamicsmentioning

confidence: 95%

Solvent dynamical effects in electron transfer: molecular dynamics simulations of reactions in methanol

1993

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“…Following the dielectric continuum model [16] one predicts a monoexponential decay with r S = (e~/eo)r D = r l, with e~ and e 0 being the dielectric constant at respectively infinite and zero frequency and "1" I is the longitudinal relaxation time. Although for several solutions this approximation has been found to hold (e.g., for dimethylformamide r S = 1.4 ps and r I = 0.8 ps [17]) more advanced modelling is necessary when deviations from the continuum theory occur,…”

Section: Piis0301-0104(96)mentioning

confidence: 99%

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

et al. 1996

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The dynamic Stokes shift of fluoroprobe in its lowest excited charge transfer state has been studied in a series of solvents, at room temperature, with a time resolution of about 300 fs. Using the fluorescent upconversion method dynamic Stokes shifts of up to 3000 cm ~ have been resolved. The Stokes shift is attributed to the solvent response to the large photoinduced dipole moment of fluoroprobe (~ 30 D) in the fluorescent charge transfer state. The solvation dynamics is determined by the rotational diffusional motions of the ethereal solvent molecules.

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“…Using time-resolved emission methods such as femtosecond fluorescence upconversion spectroscopy, this emission red shift can be time-resolved and is called the timedependent fluorescence Stokes shift (TDFSS). [12][13][14][15][16][17][18][19] The TDFSS method has been well characterized for use in probing the dynamics of the liquid state. [12][13][14][15][16][17][18][19][20] Many of the most successful studies have used 7-aminocoumarins as probes of the TDFSS.…”

Section: Introductionmentioning

confidence: 99%

Time-Dependent Density Functional Theory Investigation of the Ground and Excited States of Coumarins 102, 152, 153, and 343

2002

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We present calculations of various properties of the ground and excited electronic states of coumarins 102, 152, 153, and 343. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT), we examine the excitation energies to the S 1 and S 2 states, the ground and excited-state dipole moments, and the lowest ionization potentials of these coumarins. In the case of C153, we locate two distinct S 0 minima due to differing conformations of the julolidyl ring structure and compare properties for the syn and anti conformers. For C343, we examine the possibility of proton transfers in the ground and S 1 states of the system. We find that (1) DFT tends to overestimate the ground-state dipole moments in these systems, (2) excellent agreement is obtained between TDDFT and experimental vertical excitation energies, (3) TDDFT and CIS yield similar estimates of the dipole moment change between the S 0 and S 1 states, both of which are in the range of previous experimental estimates, (4) in each case, the S 2 state is at least 0.5 eV above the S 1 state for the ground-state geometry, and (5) proton transfer is not likely in the ground state of C343 but is only 0.18 eV higher in energy in the S 1 state. We also compare the DFT/TDDFT results with RHF/CIS, MP2, and INDO S/CI results. We find good agreement between MP2 and experimental ground-state dipole moments and good agreement between INDO S/CI and TDDFT gas-phase excitation energies.

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Nonexponential solvation dynamics of simple liquids and mixtures

Cited by 205 publications

References 37 publications

Solvent dynamical effects in electron transfer: molecular dynamics simulations of reactions in methanol

Solvent dynamical effects in electron transfer: molecular dynamics simulations of reactions in methanol

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

Time-Dependent Density Functional Theory Investigation of the Ground and Excited States of Coumarins 102, 152, 153, and 343

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