Raman spectrum of water:  transverse and longitudinal acoustic modes below .apprxeq.300 cm-1 and optic modes above .apprxeq.300 cm-1

Walrafen, G. E.

doi:10.1021/j100369a008

Cited by 181 publications

(165 citation statements)

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“…7 shows the OKE spectrum of liquid water at room temperature where the translational diffusional (cage-rattling) mode is accompanied by two modes: the hydrogen-bond bend and stretch or, equivalently, the transverse acoustic (TA) and longitudinal acoustic (LA) phonon modes. [35,[111][112][113][114] For water, with its relatively stiff bonding, these are readily identified. In Fig.…”

Section: Universal Behavior?mentioning

confidence: 99%

Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water

Turton

Hunger

Stoppa

et al. 2011

Journal of Molecular Liquids

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ÔØ Å ÒÙ× Ö ÔØThis is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Abstract. The water molecule has the convenient property that its molecular polarizability tensor is nearly isotropic while its dipole moment is large. As a result, the low-frequency anisotropic Raman spectrum of liquid water is mostly collision induced and therefore reports primarily translational motions while the far-infrared (terahertz) and dielectric spectrum is dominated by rotational modes. A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPTAtomic and globular-molecular liquids have a zero dipole moment as well as an isotropic polarizability tensor. These spectrum-simplifying properties were exploited in a study of a number of liquids and solutions using ultrafast optical Kerr-effect (OKE) spectroscopy combined with dielectric relaxation spectroscopy (DRS), terahertz time-domain spectroscopy (THz-TDS), and terahertz field-induced second-harmonic generation (TFISH) spectroscopy. For room-temperature ionic liquids (RTILs), liquid water, aqueous salt solutions, noble gas liquids, and globular molecular liquids it was found that, in each case, surprising structure and/or inhomogeneity is observed, ranging from mesoscopic clustering in RTILs to stretched exponential dynamics in the noble gas liquids. For aqueous electrolyte solutions it is shown that the viscosity, normally described by the Jones-Dole expression, can be explained in terms of a jamming transition, a concept borrowed from soft condensed matter studies of glass transitions in colloidal suspensions.

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Section: Universal Behavior?mentioning

confidence: 99%

Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water

Turton

Hunger

Stoppa

et al. 2011

Journal of Molecular Liquids

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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%

“…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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confidence: 99%

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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“…Roughly speaking the 200 cm −1 peak is related to hindered longitudinal translations of water molecules in the HB network (i.e., HB stretching vibrations) with a distinct collective character. The intermolecular vibrational modes belonging to frequencies above 300 cm −1 stem from librational (i.e., hindered rotational) motion (24,25). In Raman spectra, additional resonances around 60 cm −1 are attributed to HB bending (24,25) and contribute only weakly to the IR absorption.…”

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confidence: 99%

“…The intermolecular vibrational modes belonging to frequencies above 300 cm −1 stem from librational (i.e., hindered rotational) motion (24,25). In Raman spectra, additional resonances around 60 cm −1 are attributed to HB bending (24,25) and contribute only weakly to the IR absorption. Based on this gross picture, the frequency range probed by the aforementioned THz experiments is therefore expected to be dominated in an intricate way by HB network motion.…”

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confidence: 99%

Dissecting the THz spectrum of liquid water from first principles via correlations in time and space

Heyden

Sun

Funkner

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

400

490

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Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at ≈200 cm -1 is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm -1 ≈2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e.g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules—even in the absence of well-defined resonances.

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Raman spectrum of water: transverse and longitudinal acoustic modes below .apprxeq.300 cm-1 and optic modes above .apprxeq.300 cm-1

Cited by 181 publications

References 0 publications

Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water

Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water

Aqueous solvation dynamics studied by photon echo spectroscopy

Dissecting the THz spectrum of liquid water from first principles via correlations in time and space

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