A pump-probe experiment is described to study femtosecond dynamics of hydrogen bonds in liquid water. The key element of the experimental setup is a laser source emitting 150 fs pulses in the 2.5 -4.4 mm spectral region, at a 10 mJ power level. The OH-stretching band is recorded for different excitation frequencies and different pump-probe delay times. Time-dependent solvatochromic shifts are observed and are interpreted with the help of statistical mechanics of nonlinear optical processes. Using these spectral data, the OH · · · O motions are "photographed" in real time. [S0031-9007(98)08298-2] PACS numbers: 82.20.Wt, 78.47. + pElementary chemical processes in gases and liquids take place on time scales ranging from 10 fs to 10 ps. It took ultrafast laser technology over 20 years to reach these scales. An important breakthrough was accomplished when Zewail and his colleagues, applying laser spectroscopic methods, succeeded in following the photochemical dissociation of gaseous iodine cyanide (ICN) in real time [1], producing in this way a "photographic" picture of the process. A number of related studies were published later; see, e.g., . Although essential, this was only the first step; thermally activated chemical reactions in liquids necessitate further studies. They require the availability of femtosecond infrared sources, the knowledge of statistical mechanics of nonlinear optical processes, and that of large scale quantum molecular dynamics simulations.Published work on femtosecond dynamics of thermally activated processes mainly refers to an isotopic variety of liquid water, the diluted solution HDO͞D 2 O. The following directions of research were explored: (i) Pumpprobe experiments were realized by Graener, Seifert, and Laubereau at 10 ps [5] and by Laenen, Rauscher, and Laubereau at 1 ps [6] time scales. Hole burning of the OH-stretching band was observed for the first time and a population relaxation time of 1.5 ps was inferred. (ii) Another midinfrared pump-probe study of HDO dissolved in D 2 O, realized with polarization resolution at 250 fs time scales, was published by Woutersen, Emmerichs, and Bakker [7]. The orientational relaxation of HDO was found to be biexponential, with time constants of 0.7 and 13 ps. (iii) Theoretical work on this subject, mainly due to Bratos and Leicknam [8,9], employed the correlation function approach of statistical mechanics of nonlinear optical processes. A method was proposed to study OH · · · O motions of water in real time.The purpose of this paper is to realize the experiment suggested in Ref.[9], "photographing" H-bond motions in this way. The principle of the experiment is as follows.Its key ingredient is the well-known relation between the OH-stretching frequency and the length of an H bond; it is described in Refs. [10,11] and is illustrated in Fig. 1. Pumping the HDO͞D 2 O solution at a given frequency V 1 thus results in selecting the OH · · · O bonds of a specified length; an alternative statement is that the pump pulse generates a coherently excited wave ...

We report direct structural evidence of the bridged radical (CH2ICH2.) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with approximately 0.01 angstrom spatial resolution and approximately 100 picosecond time resolution: The loss of one iodine atom from C2H4I2 leads to the C-I-C triangular geometry of CH2ICH2.. This transient C2H4I then binds to an iodine atom to form a new species, the C2H4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

We present a time-resolved x-ray diffraction study to monitor the recombination of laser-dissociated iodine molecules dissolved in CCl4. The change in structure of iodine is followed during the whole recombination process. The deexcitation of solute molecules produces a heating of the solvent and induces tiny changes in its structure. The variations in the distance between pairs of chlorine atoms in adjacent CCl4 molecules are probed on the mA length scale. However, the most striking outcome of the present work is the experimental determination of temporally varying atom-atom pair distribution functions. Variations of the mean density of the solution during thermal expansion are also followed in real time. One concludes that not only time-resolved optical spectroscopy but also time-resolved x-ray diffraction can be used to monitor atomic motions in liquids.

A theory is proposed to study the hydrophobic hydration of rare gases and methane in water. The Ostwald absorption coefficient γ, the hydration energy ΔE, and entropy ΔS are calculated by combining large-scale molecular-dynamics simulations and test-particle methods. The convergence of calculations is checked with particular care. The structure of the first two hydration shells is analyzed in terms of appropriate pair distribution functions. The picture conveyed by this theory is compared to that provided by the early work.

An experiment is described to study temporal variations of the hydrogen bond length in diluted HDO/D2O solutions. The principles of this laser spectroscopic experiment are explained first. The construction of a laser source generating 150 fs pulses in the 2.5-4.5 microns spectral region at a 10 microJ power level is detailed next. The OH stretching band is reproduced for different excitation frequencies and different pump-probe delay times. A theory, based on statistical mechanics of nonlinear optical processes, is proposed to calculate the lowest two spectral moments. An effect is reported, the delay dependent vibrational solvatochromism. It is shown how this effect can be exploited to follow temporal variations of the OH...O bond length directly, in real time. The corresponding time scales are of the order of 700 fs. No bond oscillations are observed.

A new theory is proposed to describe spectral effects of the coupling between molecular rotations and OH¯O motions in liquid water. The correlation function approach is employed together with a special type of development in which the coupling energy of these two motions is the expansion parameter. The isotropy of the liquid medium plays an essential role in this study. Based on this theory, a new infrared pump-probe experiment is described permitting a visualization of molecular rotations at subpicosecond time scales. Full curves relating the mean squared rotational angle and time, and not only the rotational relaxation time, are measured by this experiment. However, very short times where the incident pulses overlap must be avoided in this analysis. The lifetime of OH¯O bonds in water is rotation-limited.

We study the spectral response of the transition between the first and the second excited state of the O–H stretch vibration of HDO dissolved in liquid D2O with two-color femtosecond mid-infrared spectroscopy. The spectral response of this transition differs strongly from the fundamental absorption spectrum of the O–H stretch vibration. In addition, excitation of the O–H stretch vibration is observed to lead to a change of the hydrogen-bond dynamics of liquid water. We show that both these observations can be described with a refined quantum-mechanical version of the Lippincott–Schroeder model for hydrogen-bonded OH⋯O systems.

A theory is proposed to describe the shape, in inert solutions, of hydrogen stretching ir bands of complexes with hydrogen bonds. The theory uses stochastic arguments and is related to general theories of ir band profiles of liquids. The cases of weak and medium strength hydrogen bond are treated separately. In the former case the band profile is, essentially, a broad asymmetrically distorted Gaussian produced by an anharmonic coupling between the high frequency AH stretching mode and the perturbed low frequency AH⋅⋅⋅B stretching mode. In the latter case the profile is, essentially, a very broad Gaussian intersected by a number of flat or deep, broad or narrow Evans-type transmission windows. Here, the band shaping mechanisms are the anharmonic coupling between the AH stretching and different low frequency external motions and the Fermi resonance between states involving the AH stretching and some other internal modes. Spectral manifestations of hydrogen bonded liquids represent the most extreme case of vibrational broadening and the presence of the Evans holes is its characteristic feature.