Ultrafast temperature jump studies of hydrogen bonds

Graener, H.; Ye, T. Q.

doi:10.1021/j100353a004

Cited by 15 publications

(7 citation statements)

References 2 publications

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“…The equilibrium constant in the ground state has been estimated to be 1.86 and the hydrogen-bond formation time and the lifetime of hydrogen bond have been determined to be 65 and 120 ps, respectively. The lifetime is similar to the reported 250 ps lifetime of hydrogen bonds in ethanol oligomers isolated in a non-polar solvent [109], but is much longer than the subpicosecond lifetime reported in pure water [110]. The lack of a strong viscosity dependence of the equilibration time suggested that the bond formation/breaking event was a very local motion that did not involve motion of the center of mass of the solvent molecule or largescale rearrangement of the solvent hydrogen-bond network but, rather, that only a simple rotation around the O--C bond might be involved.…”

Section: Resorufin-alcohols (Ref [54])supporting

confidence: 86%

Ultrafast Dynamics of the Excited States of Hydrogen‐Bonded Complexes and Solvation

Palit¹

2010

Hydrogen Bonding and Transfer in the Excited State

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In solutions, solute and solvent molecules interact to minimize the free-energy of the solute-solvent system [1][2][3][4][5]. Each solute molecule is surrounded by a shell of more or less tightly bound solvent molecules because of intermolecular forces between them; the phenomenon is well-known as "solvation" and "solvation energy" can be defined as the change of Gibb's free energy when a molecule is transferred from the gas phase into the solvent. Solvation interaction mainly arises due to the columbic forces between the dipoles of the solute and solvent molecules [6]. This is a long-range interaction, also known as a "non-specific" interaction, and for a particular solute molecule, the solvation energy is solely determined by the dielectric properties of the solvent. However, in addition to the dipolar solvation energy, the free energy of the solute-solvent system may be further lowered if a hydrogen bond is formed between the solute and a solvent molecule [7,8]. Since two specific solute and solvent molecules are involved in formation of the hydrogen bond, this kind of solvation interaction is known as "specific" interaction [9], which will be described here as formation of hydrogenbonded complex.Following photoexcitation of a solute molecule, the electronic charge distribution is changed. In such a case, in which the molecule is excited directly to an excited state having intramolecular charge transfer (ICT) character, the instantaneous and significant change in the polarity of the molecule following photoexcitation drives the dipoles of the surrounding solvent molecules to reorganize themselves to minimize the free energy of the solute-solvent system. This phenomenon is popularly known as "dipolar solvation" [10][11][12][13][14][15]. Following photoexcitation of the hydrogen-bonded complex formed in the ground electronic state of the solute, the

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Section: Resorufin-alcohols (Ref [54])supporting

confidence: 86%

Ultrafast Dynamics of the Excited States of Hydrogen‐Bonded Complexes and Solvation

Palit¹

2010

Hydrogen Bonding and Transfer in the Excited State

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“…These transient bleaching effects cannot be due to a shift in the dissociation-association equilibrium of the oligomers, since temperature jump studies on the EtOH:CCl 4 system have shown that the response of this equilibrium to temperature changes occurs with a time constant of 240 ps. 10 The observed decay of the bleaching can be explained if the vibrational relaxation takes place by a rapid energy transfer from the O-H stretching coordinate r OH to the hydrogen-bond coordinate r OH•••O . 8,11 The excitation energy exceeds the binding energy of the hydrogen bond, which is ϳ2000 cm Ϫ1 .…”

Section: A Hydrogen-bond Predissociationmentioning

confidence: 99%

“…1 The hydrogen bonds of alcohols in apolar solution have been the subject of numerous infrared spectroscopic studies. [2][3][4][5][6][7][8][9][10][11] The strong influence of hydrogenbond formation on the linear response of the O-H stretching mode of ethanol in apolar solution was established 50 years ago. 2 Since then, the coupling between the O-H stretching mode and the hydrogen bond in alcohol oligomers has been extensively characterized.…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5][6][7] Nevertheless, detailed knowledge about the dynamical aspects of this coupling was lacking until recently. Graener, Ye, and Laubereau [8][9][10] were the first to employ picosecond time-resolved midinfrared pump-probe spectroscopy to investigate the dynamics of the O-H stretching mode of hydrogen-bonded ethanol oligomers in dissolved CCl 4 . Their studies revealed that excitation of the O-H stretching mode of hydrogen-bonded ethanol results in a fast predissociation of the hydrogen bond, followed by a much slower reassociation process.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A femtosecond midinfrared pump–probe study of hydrogen-bonding in ethanol

Woutersen

Emmerichs

Bakker

1997

The Journal of Chemical Physics

140

160

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“…The coupling between the O--H stretching mode and the hydrogen bond in alcohol oligomers has been extensively characterized [2,3], but detailed knowledge about the dynamical aspects of this coupling was lacking until recently. Using picosecond infrared pump-probe spectroscopy, Graener, Ye and Laubereau [4][5][6] were the first to reveal that excitation of the OH stretching mode of hydrogen-bonded ethanol results in a fast predissociation of the hydrogen bond, followed by a *Corresponding author. much slower reassociation process [4].…”

Section: Introductionmentioning

confidence: 99%