Femtosecond optical Kerr effect studies of water

Palese, Stephen P.; Schilling, Lynn; Miller, R. J. Dwayne; Staver, P. Randall; Lotshaw, William T.

doi:10.1021/j100076a013

Cited by 172 publications

(187 citation statements)

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“…In addition to this mode, one or two faster relaxational modes Chemical Physics 258 (2000) 233±245 www.elsevier.nl/locate/chemphys have been reported with time constants that vary between a few hundred femtoseconds to a few picoseconds [10±16]. The origin of the relaxational modes has not been unambiguously identi®ed, and they have been assigned to the coupling between the high-frequency librational mode and lowerfrequency modes [6], to the dephasing of the stretch and bend modes of the hydrogen bonds [14] and the rotational diusion (reorientation) of the dipolar water molecules [15,16]. Recently, it has become possible to investigate the reorientational motion of liquid water in a time-resolved manner with femtosecond mid-infrared saturation spectroscopy [17].…”

Section: Introductionmentioning

confidence: 99%

Reorientational motion and hydrogen-bond stretching dynamics in liquid water

2000

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The reorientational motion of the molecules in liquid water is investigated by measuring the anisotropy decay of the O±H stretching mode of HDO dissolved in D 2 O using femtosecond mid-infrared pump±probe spectroscopy. We observe that the anisotropy shows a non-exponential decay with an initial fast component of which the amplitude increases with increasing lengths of the O±HÁ Á ÁO hydrogen bond. The experimental results can be accurately described with a model in which the dependence of the reorientation rate on the hydrogen-bond length and the stochastic modulation of this length are accounted for. It is found that the O±H group of a water molecule can only reorient after the O±HÁ Á ÁO hydrogen bond has suciently lengthened. As a result, the eective rate of reorientation of the molecules in liquid water is determined by the rate at which the length of the hydrogen bonds is modulated. Ó

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Section: Introductionmentioning

confidence: 99%

Reorientational motion and hydrogen-bond stretching dynamics in liquid water

2000

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“…[16][17][18][19][20] Experimentally, time-domain techniques such as fluorescence up-conversion, 2 optical Kerr effect ͑OKE͒ [3][4][5] and THz spectroscopy, 6,7 in addition to frequency-domain spectroscopies such as Raman [8][9][10] and infrared ͑IR͒ [11][12][13][14][15] have been employed to gain a detailed understanding of the intermolecular and intramolecular motions and dynamics of liquid water. Theoretical studies of aqueous solvation 16 have included simulations ranging from predictions of the IR and Raman spectra, [20][21][22][23] to calculations of the solvation relaxation function S(t), 17,19,23,24 and the third order response.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, a calculated third order response function, including an interactioninduced term, 26,27 concurred with experimental OKE data of pure water. 4,5 However, a solvation dynamics study has not yet experimentally resolved the influence of this dipoleinduced-dipole contribution in water.…”

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confidence: 99%

“…The intermolecular components between 0 and 1000 cm Ϫ1 in the solvation spectral density have been assigned to diffusive motions ͑ϳ2-10 cm Ϫ1 ͒, a hindered translational region of the hydrogen-bonded network ͑ϳ180 cm Ϫ1 ͒, and a broad hindered rotational ͑librational͒ band ͑ϳ600 cm Ϫ1 ͒. 16 The band observed at 60 cm Ϫ1 in the Raman [8][9][10] and OKE [3][4][5] spectra is assigned to the hydrogen bonding bend. However, its appearance in the far IR is more controversial.…”

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Aqueous solvation dynamics studied by photon echo spectroscopy

Lang

Jordanides

Song

et al. 1999

The Journal of Chemical Physics

131

160

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Three-pulse photon echo peak shift measurements were employed to study aqueous solvation dynamics. A new perspective of dielectric continuum theory [X. Song and D. Chandler, J. Chem. Phys. 108, 2594 (1998)] aided in characterizing the system-bath interactions of eosin in water. Application of this theory provides solvation energies, which were used within the spectral density representation ρ(ω), to calculate the experimental peak shift. Simulations with only solvation contributions to ρ(ω), where a substantial amplitude of the solvation occurs within ∼30 fs, are remarkably consistent with our data. Furthermore, simulations using this theoretical solvation spectral density and an experimentally determined intramolecular spectral density yield an excellent total simulation of the peak shift data over the entire dynamic range. Our experimental results substantiate predictions that interaction-induced polarizability effects, contributing via a ∼180 cm−1 band in the spectral density, influence the initial dynamics. Three-pulse photon echo peak shift measurements were employed to study aqueous solvation dynamics. A new perspective of dielectric continuum theory ͓X. Song and D. Chandler, J. Chem. Phys. 108, 2594 ͑1998͔͒ aided in characterizing the system-bath interactions of eosin in water. Application of this theory provides solvation energies, which were used within the spectral density representation ͑͒, to calculate the experimental peak shift. Simulations with only solvation contributions to ͑͒, where a substantial amplitude of the solvation occurs within ϳ30 fs, are remarkably consistent with our data. Furthermore, simulations using this theoretical solvation spectral density and an experimentally determined intramolecular spectral density yield an excellent total simulation of the peak shift data over the entire dynamic range. Our experimental results substantiate predictions that interaction-induced polarizability effects, contributing via a ϳ180 cm Ϫ1 band in the spectral density, influence the initial dynamics.

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“…More recently, new experimental developments based on ultrafast laser techniques have made it possible to investigate intermolecular dynamical processes of water at much shorter timescales with substantially higher level of detail. Among these, terahertz spectroscopy [12] and nonlinear optical methods such as Raman echo [13] and optical Kerr effect (OKE) [14] spectroscopies stand out for providing remarkably valuable information directly in the time domain.…”

Section: Introductionmentioning

confidence: 99%