Dissimilar Dynamics of Coupled Water Vibrations

Jansen, Thomas L. C.; Cringus, Dan; Pshenichnikov, Maxim S.

doi:10.1021/jp900480r

Cited by 51 publications

(77 citation statements)

References 46 publications

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“…Cringus et al explained the prominent spectral dependence of the anisotropy in the frame of splitting of OH-oscillator vibrations into symmetric and asymmetric modes. 45,79 Similar effects were also reported in the IR studies of weakly hydrated membranes. 73 It was proposed that the presence of ultrafast exchange between different modes provides evidence for both OH oscillators being in a similar hydrogen-bonded configuration-both either bonded or nonbonded to neighboring water molecules.…”

Section: Methodssupporting

confidence: 80%

“…45,79 The initial negative anisotropies at the frequencies of other transitions cannot be explained in a single-transition framework but is fully consistent with the model of two communicating orthogonal modes as it is the case for the symmetric and asymmetric modes of the H 2 O molecule (note that although this designation is not entirely accurate because the modes are not fully delocalized 79 we will use it anyway for briefness). The observed anisotropy data are in line with those previously reported for diluted H 2 O solutions where intermolecular coupling between OH oscillators of different water molecules was inhibited by either nonpolar 80 or moderately polar 45,79 solvents. Cringus et al explained the prominent spectral dependence of the anisotropy in the frame of splitting of OH-oscillator vibrations into symmetric and asymmetric modes.…”

Section: Methodssupporting

confidence: 69%

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Reduced coupling of water molecules near the surface of reverse micelles

Bakulin

Pshenichnikov

2011

Phys. Chem. Chem. Phys.

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Section: Methodssupporting

confidence: 80%

Section: Methodssupporting

confidence: 69%

Reduced coupling of water molecules near the surface of reverse micelles

Bakulin

Pshenichnikov

2011

Phys. Chem. Chem. Phys.

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“…In order to explain spectacular features in frequency shifts, band shapes, and bandwidths of the components the OH stretching modes the linear and nonlinear response theory [43][44][45], quantum ab inito calculations for possible cluster structures [62][63][64][65][66][67][68], classical [69][70][71][72][73] and mixed quantum/classical molecular dynamics simulations [74][75][76] have been used.…”

Section: Discussionmentioning

confidence: 99%

Hydrogen bonds of interfacial water in human breast cancer tissue compared to lipid and DNA interfaces

Abramczyk¹,

Brożek-Płuska²,

Surmacki³

et al. 2011

JBPC

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The paper presents the results for water confined in a human breast cancerous tissue, a single stranded DNA, a double stranded DNA and in phospholipids (DPPC-D--Phosphatidylcholine, dipalmitoyl). The interfacial water in DNA and lipids is represented by a double band in the region of the OH stretching mode of water corresponding to the symmetric and asymmetric vibrational modes, in contrast to water confined in the cancerous breast tissue where only one band at 3311 cm -1 has been recorded. The marked red-shift of the maximum peak position of the OH stretching mode confirms that the vibrational properties of the interfacial water observed in restricted biological environment differ drastically from those in bulk water. The change of vibrational pattern of behavior may be due to the decoupling of the vibrations of the OH bonds in water molecule or change of the vibrational selection rules at biological interfaces. According to our knowledge Raman vibrational properties of water confined in the normal and cancerous breast tissue of the same patient have not been reported in literature yet. Here we have also presented the first Raman 'optical biopsy' images of the non-cancerous and cancerous (infiltrating ductal cancer) human breast tissues.

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“…The Q-model predicts distinctions between S σ,i (t), S Ω,i (t), and S 2,i (t) calculated in the same electronic state (eq (29)). All these predictions go beyond the standard expectations of L-models, 40,41,43 implying that the dynamics are nonlinear.…”

Section: Dynamicsmentioning

confidence: 99%

“…21,24,29 There is also growing evidence that these non-Gaussian dynamics might be linked to quadratic solute-solvent coupling. The statistics of the vibrational frequency has been successfully mapped on the statistics of the medium electric field E projected on the direction of vibrational stretch.…”

Section: Introductionmentioning

confidence: 99%

Non-Gaussian Lineshapes and Dynamics of Time-Resolved Linear and Nonlinear (Correlation) Spectra

Dinpajooh

Matyushov

2014

J. Phys. Chem. B

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Signatures of nonlinear and non-Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are analyzed in a model considering a linear plus quadratic dependence of the spectroscopic transition frequency on a Gaussian nuclear coordinate of the thermal bath (quadratic coupling). This new model is contrasted to the commonly assumed linear dependence of the transition frequency on the medium nuclear coordinates (linear coupling). The linear coupling model predicts equality between the Stokes shift and equilibrium correlation functions of the transition frequency and time-independent spectral width. Both predictions are often violated, and we are asking here the question of whether a nonlinear solvent response and/or non-Gaussian dynamics are required to explain these observations. We find that correlation functions of spectroscopic observables calculated in the quadratic coupling model depend on the chromophore's electronic state and the spectral width gains time dependence, all in violation of the predictions of the linear coupling models. Lineshape functions of 2D spectra are derived assuming Ornstein-Uhlenbeck dynamics of the bath nuclear modes. The model predicts asymmetry of 2D correlation plots and bending of the center line. The latter is often used to extract two-point correlation functions from 2D spectra. The dynamics of the transition frequency are non-Gaussian. However, the effect of non-Gaussian dynamics is limited to the third-order (skewness) time correlation function, without affecting the time correlation functions of higher order. The theory is tested against molecular dynamics simulations of a model polar-polarizable chromophore dissolved in a force field water.

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Dissimilar Dynamics of Coupled Water Vibrations

Cited by 51 publications

References 46 publications

Reduced coupling of water molecules near the surface of reverse micelles

Reduced coupling of water molecules near the surface of reverse micelles

Hydrogen bonds of interfacial water in human breast cancer tissue compared to lipid and DNA interfaces

Non-Gaussian Lineshapes and Dynamics of Time-Resolved Linear and Nonlinear (Correlation) Spectra

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