Solvent-Shift Effects on Electronic Spectra and Excited-State Dipole Moments and Polarizabilities

Amos, A. T.; Burrows, B. L.

doi:10.1016/s0065-3276(08)60566-3

Cited by 180 publications

(103 citation statements)

References 21 publications

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“…For the purpose of this paper, we shall focus our attention on polar molecules (i.e., those with nonzero ground-state dipole moments). In this case, the dominant effect associated with the shift is related to changes of the dipole moments upon excitation [4,5] All existing theories relate the solvent shift to weak interactions between a solute molecule and a solvent, usually treated as an isotropic dielectric medium characterized by its static relative electric permittivity (ε) and refractive index (n). The parameter taken as a measure of the shift is either the difference between the positions of the lowest-energy absorption bands of an isolated molecule and that dissolved in a given solvent [9], or the difference between the positions of the lowest-energy bands in absorption and fluorescence [10,11].…”

Section: The Solvatochromic Effectmentioning

confidence: 99%

“…(cf., e.g. [4,5,12] and references therein). In the analysis of the results reported in this paper, we shall employ the equations resulting from the theory put forward by Abe [9].…”

Section: The Solvatochromic Effectmentioning

confidence: 99%

“…Apart from an obvious oversimplification made on approximating the actual shape of molecule by a sphere, the estimation of α itself may be a source of significant errors. A plausible approximation for α, valid for 1/2ru < r s < 2ru, is [4] where ru and rs are the radii of the solute and solvent molecules, respectively, estimated from appropriate densities (p) and molar masses (M) ΝΑ being Avogadro's number. In Eqs.…”

Section: The Solvatochromic Effectmentioning

confidence: 99%

“…Among several existing methods allowing one to obtain such information, the simplest (although not the mo8t reliable) one is that making use of the solvatochromic effect (e.g. [4,5] and references therein).…”

Section: Introductionmentioning

confidence: 99%

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Solvatochromic Effect in a Benzimidazole-Based Betaine: Determination of the Dipole Moments and Second-Order Hyperpolarizability

et al. 1995

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Results of measurements of the solvent-dependent shift of the low-energy absorption band solvatochromic effect in a benzimidazole-based betaine are reported in the paper. Measurements of absorption spectra in several solvents of different polarities were performed. The solvatochromic shift of the low-lying absorption band was found to exceed 3000 cm -1 ; the results obtained were then employed to calculate the ground-and excited-state dipole moment of the molecule. The spectroscopic measurements were supplemented by measurements of the ground-state dipole moment. A remarkable change in the charge distribution was found to occur upon the electronic excitation: both the experimental results and the calculations indicate that the ground-state dipole moment is close to 13 D, whereas in the excited state it amounts to ca. 3 D. The second-order hyperpolarizability of the molecule was calculated from the measurements; its off-resonance value amounts to ca. 20 x 10 -40 m4 /V (4.8 x 10 -30 esu), depending on the solvent used.

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Section: The Solvatochromic Effectmentioning

confidence: 99%

“…(cf., e.g. [4,5,12] and references therein). In the analysis of the results reported in this paper, we shall employ the equations resulting from the theory put forward by Abe [9].…”

Section: The Solvatochromic Effectmentioning

confidence: 99%

Section: The Solvatochromic Effectmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Solvatochromic Effect in a Benzimidazole-Based Betaine: Determination of the Dipole Moments and Second-Order Hyperpolarizability

et al. 1995

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“…(8)(9)(10) Shirota et al (11,12) observed that the addition of alcohols to the naphthalene (NP)-TEA system in acetonitrile (AN) reduced both the bimolecular rate constants for the quenching by triethylamine (TEA) and the quantum yields of the photoinduced reactions, and suggested that the hydrogen-bonding interaction between the amine and alcohol suppressed the electron-transfer process owing to the decrease in the concentration of free TEA. Since AN was used as a solvent in their study, the effect of alcohols on the emission from the exciplex could not be examined.…”

Section: Introductionmentioning

confidence: 99%

Polar and Hydrogen-Bonding Effects of Alcohols on the Emission Spectrum of Styrene–Triethylamine System

2005

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The emission spectra of styrene (ST)-triethylamine (TEA) systems were measured under steady-state illumination conditions in some tetrahydrofuran (THF)-protic solvent mixtures. The fluorescence spectrum of the ST-TEA system in THF consists of two bands (band A at 304 nm (fluorescence of ST) and band B at 460 nm (emission from an exciplex)). The intensity of band A increased and that of band B decreased with increasing amounts of protic solvents in THF-protic solvent mixtures. The increase in the intensity of band A was explained by the decrease in the concentration of free amine owing to the hydrogen-bonding interaction (or protonation) between TEA and protic solvents. The decrease in the intensity of band B was considered to be caused by the decrease in the concentration of free amine upon the addition of protic solvents and the enhanced conversion of the exciplex to an ion pair with increasing solvent polarity. The polar effect was expressed as a function of the relative permittivity of the solution.

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Solvatochromism of the ?* ?n transition of acetone by combined quantum mechanical?classical mechanical calculations

Vries

Duijnen

1996

Int. J. Quantum Chem.

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rnThe solvent shift of the T * + n transition of acetone in water, acetonitrile, and tetrachloromethane was calculated in a combined quantum mechanical-classical mechanical approach, using both dielectric continuum and explicit, polarizable molecular solvent models. The explicit modeling of solvent polarizability allows for a separate analysis of electrostatic, induction, and dispersion contributions to the shifts. The calculations confirm the qualitative theories about the mechanisms behind the blue shift in polar solvents and the red shift in nonpolar solvents, the solvation of the ground state due to electrostatic interactions being preferential in the former, and favorable dispersion interaction with the excited state, in the latter case. Good quantitative agreement for the solvent shift between experiment ( + 1,700, + 400, and -350 cm-' in water, acetonitrile, and tetrachloromethane, respectively) and the explicit solvent model ( + 1,821, + 922, and tive characterization of the various solvents. Solvent polarity scales derived from electronic transitions have served in correlating structure and activity in many areas of chemistry. The computation of solvent effects from molecular models has followed the qualitative theories in an attempt to quantify the parameters appearing in the theory [4,5]. Standard models are based

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Solvent-Shift Effects on Electronic Spectra and Excited-State Dipole Moments and Polarizabilities

Cited by 180 publications

References 21 publications

Solvatochromic Effect in a Benzimidazole-Based Betaine: Determination of the Dipole Moments and Second-Order Hyperpolarizability

Solvatochromic Effect in a Benzimidazole-Based Betaine: Determination of the Dipole Moments and Second-Order Hyperpolarizability

Polar and Hydrogen-Bonding Effects of Alcohols on the Emission Spectrum of Styrene–Triethylamine System

Solvatochromism of the ?* ?n transition of acetone by combined quantum mechanical?classical mechanical calculations

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