Modulated super-Gaussian laser pulse to populate a dark rovibrational state of acetylene.

A pulse-shaping technique in the mid-infrared spectral range based on pulses with a super-Gaussian temporal profile is considered for laser control. We show a realistic and efficient path to the population of a dark rovibrational state in acetylene (C2H2). The laser-induced dynamics in C2H2 are simulated using fully experimental structural parameters.

Laser control of a dark vibrational state of acetylene in the gas phase-Fourier transform pulse shaping constraints and effects of decoherence.

We propose a methodology to tackle the laser control of a non-stationary dark ro-vibrational state of acetylene (CH), given realistic experimental limitations in the 7.7 μm (1300 cm) region. Simulations are performed using the Lindblad master equation, where the so-called Lindblad parameters are used to describe the effect of the environment in the dilute gas phase.

Lindblad parameters from high resolution spectroscopy to describe collision-induced rovibrational decoherence in the gas phase-Application to acetylene.

Within the framework of the Lindblad master equation, we propose a general methodology to describe the effects of the environment on a system in the dilute gas phase. The phenomenological parameters characterizing the transitions between rovibrational states of the system induced by collisions can be extracted from experimental transition kinetic constants, relying on energy gap fitting laws. As the availability of these kinds of experimental data can be limited, this work relied on experimental line broadening coefficients, however still using energy gap fitting laws.

Reactivity of Hydrated Hydroxide Anion Clusters with H and Rb: An ab Initio Study.

We present a theoretical investigation of the hydrated hydroxide anion clusters, OH(HO), and of the collisional complexes, H-OH(HO) and Rb-OH(HO) (with = 1-4). The MP2 and CCSD(T) methods are used to calculate interaction energies, optimized geometries, and vertical detachment energies. Parts of the potential energy surfaces are explored with a focus on the autodetachment region.

Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH.

We have performed a systematic ab initio study on alkali and alkaline earth hydroxide neutral (MOH) and anionic (MOH) species where M = Li, Na, K, Rb, Cs or Be, Mg, Ca, Sr, Ba. The CCSD(T) method with extended basis sets and Dirac-Fock relativistic effective core potentials for the heavier atoms has been used to study their equilibrium geometries, interaction energies, electron affinities, electric dipole moment, and potential energy surfaces. All neutral and anionic species exhibit a linear shape with the exception of BeOH, BeOH, and MgOH, for which the equilibrium structure is found to be bent.

Using a direct simulation Monte Carlo approach to model collisions in a buffer gas cell.

A direct simulation Monte Carlo (DSMC) method is applied to model collisions between He buffer gas atoms and ammonia molecules within a buffer gas cell. State-to-state cross sections, calculated as a function of the collision energy, enable the inelastic collisions between He and NH to be considered explicitly. The inclusion of rotational-state-changing collisions affects the translational temperature of the beam, indicating that elastic and inelastic processes should not be considered in isolation.

Ab initio study of reactive collisions between Rb((2)S) or Rb((2)P) and OH(-)((1)Σ(+)).

A theoretical rate constant for the associative detachment reaction Rb((2)S) + OH(-)((1)Σ(+)) → RbOH((1)Σ(+)) + e(-) of 4 × 10(-10) cm(3) s(-1) at 300 K has been calculated. This result agrees with the experimental rate constant of 2-1 (+2)×10(-10)cm(3)s(-1) obtained by Deiglmayr et al. [Phys.

Simulation of the elementary evolution operator with the motional states of an ion in an anharmonic trap.

Following a recent proposal of L. Wang and D. Babikov [J.

Peculiar properties of homoleptic Cu complexes with dipyrromethene derivatives.

In view of preparing Cu polynuclear complexes with dipyrromethene ligands, the mononuclear complexes [Cu(II)(dipy)2] (dipyH = 5-phenyldipyrromethene) and [Cu(II)(dpdipy)2] (dpdipyH = 1,5,9-triphenyldipyrromethene) have been prepared and characterized by X-ray crystallography, mass spectrometry and EPR spectroscopy. Their peculiar redox and spectroscopic (absorption/emission) behaviours are discussed. In contrast to Cu(II) complexes of 1,1'-bidypyrrin, the reduction electrolysis of [Cu(II)(dpdipy)2] leads to decomposition products on a time scale of a few hours.

Density functional theory interpretation of the 1H photo-chemically induced dynamic nuclear polarization enhancements characterizing photoreduced polyazaaromatic Ru(II) coordination complexes.

The unprotonated and protonated monoreduced forms of the polyazaaromatic Ru(II) coordination complexes [Ru(tap)(3)](2+) and [Ru(tap)(2)(phen)](2+) (tap = 1,4,5,8-tetraazaphenanthrene ; phen = 1,10-phenanthroline), that is, [Ru(tap)(3)](*+), [Ru(tap)(2)(phen)](*+), [Ru(tap)(2)(tap-H)](*2+), and [Ru(tap)(tap-H)(phen)](*2+), were studied by Density Functional Theory (DFT). The electron spin density of these radical cations, the isotropic Fermi-contact, and the anisotropic dipolar contributions to the hyperfine coupling constants of the H nuclei were calculated in vacuo and using a continuum model for water solvation. For [Ru(tap)(2)(phen)](*+), as well as for its protonated form, the DFT results show that the unpaired electron is not localized on the phen ligand.