2008
DOI: 10.1021/jp0770460
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Excited State Intramolecular Charge Transfer Reaction in Binary Mixtures of Water and Tertiary Butanol (TBA):  Alcohol Mole Fraction Dependence

Abstract: The excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) has been studied in water-tertiary butanol (TBA) mixtures at different alcohol mole fractions by using steady state and time-resolved fluorescence spectroscopy. The ratio between the areas under the locally excited (LE) and charge transferred (CT) emission bands is found to exhibit a sharp rise at alcohol mole fraction approximately 0.04, a value at which several thermodynamic properties of this mixture is known to … Show more

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Cited by 58 publications
(90 citation statements)
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“…Similar alcohol mole fraction dependence is also found in our earlier studies for the quantum yield of a TICT molecule in TBA-water mixtures. 59,65 The following relation has been used to determine the radiative rate: 61 k rad = φ/〈τ〉, where the average lifetime (〈τ〉) has been calculated by using the relation, 61 …”
Section: Steady State Studiesmentioning
confidence: 99%
See 1 more Smart Citation
“…Similar alcohol mole fraction dependence is also found in our earlier studies for the quantum yield of a TICT molecule in TBA-water mixtures. 59,65 The following relation has been used to determine the radiative rate: 61 k rad = φ/〈τ〉, where the average lifetime (〈τ〉) has been calculated by using the relation, 61 …”
Section: Steady State Studiesmentioning
confidence: 99%
“…The fact that the alcohol induced modification of the Hbonding structure has small but non-negligible effects on the emission transition moment is also seen in our earlier studies with a different probe molecule in TBA-water mixture. 65 However, once the tetrahedral-like H-bonding network structure of water is disrupted and chain-like structure of alcohol appears at higher alcohol concentration, the emission transition moment becomes almost insensitive to the alcohol mole fraction (between 0⋅10 and 1⋅0). The near insensitivity of the emission transition moment on the average polarity of the medium has also been observed earlier with a different probe in neat solvents 61 and also in electrolyte solutions.…”
Section: Mole Fractionmentioning
confidence: 99%
“…Examples of such non-ideal behavior in the binary mixture of water and amphiphilic solutes are varied and well-studied [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Sometimes the anomaly is strongest at surprisingly low solute concentrations.…”
Section: Introductionmentioning
confidence: 99%
“…The TICT molecule that we have used in the present study is 4-(1-azetidinyl) benzonitrile (P4C). Since the details of TICT mechanism has been discussed elsewhere, [8][9][10][11][12][13][14] we refer to the schemes 1 and 2 in reference 8 to briefly discuss the reaction mechanism. As shown in these schemes, photo-excitation promotes P4C to the locally excited (LE) state in the first excited electronic surface (S 1 ) which is relatively less polar and possesses charge distribution probably similar to that in the ground state.…”
Section: Introductionmentioning
confidence: 99%
“…Since the TICT reactions have been found to couple partially to the medium dynamics, [8][9][10][11][12] one naturally asks the following question: What could be the effects of the observed ~10-20% slowing down of the long time solvation rate in deuterated solvents on the TICT reactions occurring in these solvents? More precisely, would the reaction rate in isotopically substituted solvents be slowed down accordingly?…”
Section: Introductionmentioning
confidence: 99%