Jean-Claude Leicknam

Transient absorption of vibrationally excited water

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.

Infrared study of diluted solutions of polyatomic molecules. I. Band shape of fundamentals associated with nondegenerate normal modes

A theory is proposed to analyze the band shapes of the simplest class of ir band profiles of polyatomic molecule solutions. The following theoretical points are explored in detail: dependence of vibrational correlation functions on the nature of normal modes involved, calculation of vectorial correlation functions for a classical ensemble of free asymmetric rotators, construction of extended diffusion models for asymmetric tops, and use of the ordered cumulant expansion techniques to study anisotropic rotational diffusion in liquids. The theory predicts a large variety of complex, often highly irregular, band profiles. A catalogue of representative band profiles is presented which orders them according to the symmetry of the active molecule.

Filming the Birth of Molecules and Accompanying Solvent Rearrangement

Molecules are often born with high energy and large-amplitude vibrations. In solution, a newly formed molecule cools down by transferring energy to the surrounding solvent molecules. The progression of the molecular and solute-solvent cage structure during this fundamental process has been elusive, and spectroscopic data generally do not provide such structural information. Here, we use picosecond X-ray liquidography (solution scattering) to visualize time-dependent structural changes associated with the vibrational relaxation of I(2) molecules in two different solvents, CCl(4) and cyclohexane. The birth and vibrational relaxation of I(2) molecules and the associated rearrangement of solvent molecules are mapped out in the form of a temporally varying interatomic distance distribution. The I-I distance increases up to ~4 Å and returns to the equilibrium distance (2.67 Å) in the ground state, and the first solvation cage expands by ~1.5 Å along the I-I axis and then shrinks back accompanying the structural change of the I(2) molecule.

Time-resolved observation of the Eigen cation in liquid water

Experimental observation and time relaxation measurement of the hydrated proton Eigen form [H(3)O(+)(H(2)O)(3)] are presented here. Vibrational time-resolved spectroscopy is used with an original method of investigating the proton excess in water. The anharmonicity of the time-resolved spectra is characteristic of the Eigen-type proton geometry. Proton relaxation occurs in less than 200 fs. A calculation of the potential energy confirms the experimental result and the Eigen cation lifetime is in good agreement with previous molecular dynamics simulations.

Ir spectra of polyatomic molecule solutions: Asymmetric tops

Abstract The IR band profiles of diluted asymmetric top molecule solutions are discussed in detail. They depend on the symmetry of the molecular top, on the direction of the transition moment and on the strength of the solventsolute interaction. A gradual transformation of the profile is observed with Increasing intermolecular perturbation. The sharp details characteristic of free rotation are blurred first and the wings collapse later. Both, vibrational and rotational band shaping mechanisms are operative in general.

Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

The published work on H bond dynamics mainly refers to diluted solutions HDO/D2O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.