The Vibrational Spectroscopy and Dynamics of Weakly Bound Neutral Complexes

Miller, R. E.

doi:10.1126/science.240.4851.447

Cited by 269 publications

(125 citation statements)

References 66 publications

(37 reference statements)

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“…38,39 This relation shows a stronger frequency dependence of the T 1 at blue frequencies compared to red frequencies, but this nonlinearity was found to be far too strong to be in accordance with our experimental data. The formula was derived for the case of vibrational predissociation, in which vibrational energy can be transferred to the O¯O hydrogen bond stretch coordinate only.…”

Section: ͑1͒supporting

confidence: 80%

Vibrational dynamics of ice in reverse micelles

Dokter

Petersen

Woutersen

et al. 2008

The Journal of Chemical Physics

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The ultrafast vibrational dynamics of HDO : D 2 O ice at 180 K in anionic reverse micelles is studied by midinfrared femtosecond pump-probe spectroscopy. Solutions containing reverse micelles are cooled to low temperatures by a fast-freezing procedure. The heating dynamics of the micellar solutions is studied to characterize the micellar structure. Small reverse micelles with a water content up to approximately 150 water molecules contain an amorphous form of ice that shows remarkably different vibrational dynamics compared to bulk hexagonal ice. The micellar amorphous ice has a much longer vibrational lifetime than bulk hexagonal ice and micellar liquid water. The vibrational lifetime is observed to increase linearly from 0.7 to 4 ps with the resonance frequency ranging from 3100 to 3500 cm −1 . From the pump dependence of the vibrational relaxation the homogeneous linewidth of the amorphous ice is determined ͑55Ϯ 5 cm −1 ͒.

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Section: ͑1͒supporting

confidence: 80%

Vibrational dynamics of ice in reverse micelles

Dokter

Petersen

Woutersen

et al. 2008

The Journal of Chemical Physics

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“…This relation results from quantum-mechanical calculations on the coupling between the hydrogen bond and the OH stretch vibration, 31 and was verified for a wide range of hydrogenbonded complexes 27 and for HDO molecules dissolved in D 2 O. 28 From the results of Fig.…”

Section: 29mentioning

confidence: 72%

“…Indeed, it has been found before that the value of T 1 decreases with decreasing OH stretch frequency, as a result of the accompanying increase of the strength of the OH¯O hydrogen-bond interaction. 27,28 B. Dynamics at small delays Most of the pump-probe delay scans shown in Fig. 4 deviate strongly from single-exponential decays and decay significantly faster at small delays than at large delays.…”

mentioning

confidence: 95%

Dynamics of water molecules in an alkaline environment

Nienhuys

Lock

Santen

et al. 2002

The Journal of Chemical Physics

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We report on a two-color mid-infrared pump-probe spectroscopic study of the dynamics of the OH stretch vibrations of HDO molecules dissolved in a concentrated ͑10 M͒ solution of NaOD in D 2 O. We observe that spectral holes can be created in the broad OH stretch absorption band that change neither position nor width on a picosecond time scale. This behavior differs strongly from that of pure HDO:D 2 O where rapid spectral diffusion ( c Ϸ600 fs) occurs. The long-living inhomogeneity indicates that a concentrated aqueous NaOX (XϭH,D) solution has a very static hydrogen-bond network. The results also show that the absorption band of the OH stretch vibration consists of two separate classes of OH groups with very different vibrational lifetimes. For component I, the lifetime of the OH stretch vibration is ϳ600 fs and increases with OH frequency, which can be explained from the accompanying decrease in the strength of the hydrogen-bond interaction. This component represents HDO molecules of which the OH group is bonded to a D 2 O molecule via a DO-H¯OD 2 hydrogen bond. For component II, the lifetime is ϳ160 fs, and does not show a significant frequency dependence. This component represents HDO molecules that are hydrogen bonded to a D 2 O molecule or an OD Ϫ ion. The short, frequency-independent vibrational lifetime of component II can be explained from the participation of the HDO molecule and its hydrogen-bonded partner in deuteron and/or proton-transfer processes.

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“…The blue shift of the OH vibrational frequency is usually attributed to weaker (on average) hydrogen bonds between the water molecules. 74,75 In the d = 1 nm reverse micelles 90% of water molecules border the lipid wall, hence the observed blue shift of the OH stretch indicates a strongly weakened hydrogenbond environment near the water-AOT interface.…”

Section: Methodsmentioning

confidence: 99%