Direct infrared absorption spectroscopy of benzene dimer.

The direct infrared (IR) absorption spectrum of benzene dimer formed in a free-jet expansion was recorded in the 3.3 μm region for the first time. This has led to the observation of the C-H stretching fundamental mode ν(13) (B(1u)), which is both IR and Raman forbidden in the monomer.

Vibrational spectra of cyclopentadienylphosphine: infrared and theoretical studies from DFT anharmonic potentials.

Both experimental and theoretical infrared investigations of cyclopentadienylphosphine (CpP) are reported. The infrared spectra (3500-500 cm(-1)) in the gas phase have been recorded at 0.5 cm(-1) resolution.

Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes.

A remarkable number of reactions between neutral free radicals and neutral molecules have been shown to remain rapid down to temperatures as low as 20 kelvin. The rate coefficients generally increase as the temperature is lowered. We examined the reasons for this temperature dependence through a combined experimental and theoretical study of the reactions of O(3P) atoms with a range of alkenes.

Laboratory measurements of the recombination of PAH ions with electrons: implications for the PAH charge state in interstellar clouds.

Laboratory measurements of the recombination of polycyclic aromatic hydrocarbon (PAH) ions with electrons are presented. Experimental data have been obtained at room temperature for azulene (C10H8) and acenaphthene (C12H10) cations by the Flowing Afterglow with PhotoIons method. The results confirm that the recombination of PAH ions is fast although well below the geometrical limit.

Study of the C(3P) + OH(X2Pi) --> CO(X1Sigma(g)+) + H(2S) reaction: a fully global ab initio potential energy surface of the X2A' state.

The C((3)P) + OH(X (2)Pi) --> CO(X (1)Sigma(g)(+)) + H((2)S) reaction has been investigated by ab initio electronic structure calculations of the X(2)A' state based on the multireference (MR) internally contracted single and double configuration interaction (SDCI) method plus Davidson correction (+Q) using Dunning aug-cc-pVQZ basis sets. In particular, the multireference space is taken to be a complete active space (CAS). Improvement over previously proposed potential energy surfaces for HCO/COH is obtained in the sense that present surface describes also the potential part where the CO interatomic distance is large.

Theoretical spectroscopy of the calcium dimer in the A 1Sigma(u)+, c3Pi(u), and a3Sigma(u)+ manifolds: an ab initio nonadiabatic treatment.

Nonadiabatic theory of molecular spectra of diatomic molecules is presented. It is shown that in the fully nonadiabatic framework, the rovibrational wave functions describing the nuclear motions in diatomic molecules can be obtained from a system of coupled differential equations. The rovibrational wave functions corresponding to various electronic states are coupled through the relativistic spin-orbit coupling interaction and through different radial and angular coupling terms, while the transition intensities can be written in terms of the ground state rovibrational wave function and bound rovibrational wave functions of all excited electronic states that are electric dipole connected with the ground state.

Infrared spectra of a species of astrochemical interest: aminoacrylonitrile (3-amino-2-propenenitrile).

Ammonia easily reacts on cyanoacetylene in the gas phase or in a solvent to form the Z- and E-isomers of aminoacrylonitrile (3-amino-2-propenenitrile, 2). This kinetically stable enamine presents interest for its possible presence in the interstellar medium, the comets, the atmospheres of Planets including the Primitive Earth, and from a theoretical point of view. B3LYP/6-311+G(3df,2p) and G2 calculations indicate that the imine isomer is significantly less stable than the enamine 2.

Photoionization-induced dynamics of ammonia: ab initio potential energy surfaces and time-dependent wave packet calculations for the ammonia cation.

An analytical anharmonic six-dimensional three-sheeted potential energy surface for the ground and first excited states of the ammonia cation has been developed which is tailored to model the ultrafast photoinduced dynamics. Selected ab initio cuts, obtained by multireference configuration interaction calculations, have been used to determine the parameters of a diabatic representation for this Jahn-Teller and pseudo-Jahn-Teller system. The model includes higher-order coupling terms both for the Jahn-Teller and for the pseudo-Jahn-Teller matrix elements.

Biopolymers: shape memory in spider draglines.

The ductility and strength of spider draglines means that they outperform the best synthetic fibres, but surprisingly little is known about the torsional properties of this remarkable filament. Unlike a mountain climber swinging from a rope, a spider suspended from its silk thread hardly ever twists. Here we show that a spider dragline has a torsional shape 'memory' in that it can reversibly and totally recover its initial form without any external stimulus; its observed relaxation dynamics indicate that these biological molecules have successively different torsional constants.

An experimental study of the intersystem crossing and reactions of C2(X1Sigmag+) and C2(a3Pi(u)) with O2 and NO at very low temperature (24-300 K).

A low-temperature gas-phase kinetics study of the reactions and collisional relaxation processes involving C2(X1Sigma(g)+) and C2(a3Pi(u)) in collision with O2 and NO partners at temperatures from 300 to 24 K is reported. The experiments employed a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) apparatus to attain low temperatures. The C2 species were created using pulsed laser photolysis at 193 nm of mixtures containing C2Cl4 diluted in N2, Ar, or He carrier gas.

Global 1 1A" potential energy surface of CH2 and quantum dynamics of a sideways insertion mechanism for the C(1D) + H2 --> CH(2pi) + H reaction.

A global adiabatic potential energy surface (PES) corresponding to the second singlet state 1 1A" (1 1B1) of CH2 has been computed in a similar way as the first singlet state 1 1A' in our previous work [B. Bussery-Honvault et al., J.

Electron attachment on HI and DI in a uniform supersonic flow: thermalization of the electrons.

In order to check the electron thermalization in the CRESU technique (Cinetique de Reaction en Ecoulement Supersonique Uniforme, e.g., "reaction kinetics in a uniform supersonic flow"), electron attachment on HI and DI has been studied in the 48-170 K range.