Classical theory of vibration energy transfer in collinear collisions

Classical theory of collisions is cast in a form which also includes the uncertainty principle. This theory is used for analyzing the vibration energy transfer in the collinear collision which approximates the He-H₂ system. The results are compared with the quantum calculations and several classical and semiclassical approaches. Very good agreement with quantum theory is found, for all the parameters investigated.     

Zeeman relaxation of N2 + (2Σ+) in collisions with 3He and 4He

We compare the cross sections for the transitions changing the projection of the total angular momentum of N₂ ⁺(²Σ) in collisions with ³He and ⁴He at very low collision energy. The fundamental states of the two nuclear spin isomers of N₂ ⁺ are considered as well as the two fine structure levels of the first excited para level N=2. It is shown that the two fundamental states of the two nuclear spin isomers behave differently. For the fundamental para level N=0 of N₂ ⁺, the projection changing cross section is always negligible compared to the elastic one for both He isotopes. For the fundamental ortho level N=1 of N₂ ⁺, the spin-rotation interaction couples the different spin levels directly so the spin relaxation becomes a first order process. The associated resonances increase the projection changing cross section which remains smaller but becomes comparable with the elastic one. This is in contrast with the excited rotational levels of N₂ ⁺, which for the rotational deactivation and elastic channels are found to be equal around the resonances for the collisions involving ³He. These two channels are always larger than the projection changing one. We also find that, for transitions involving the fundamental rotational state, the domain of validity of the threshold laws discussed by Krems and Dalgarno [Phys. Rev. A 67, 050704 (2003)] for a potential decreasing faster than 1/r2 is shortened, due to the long range charge induced dipole potential. This effect is illustrated for the collisions of ³He with the fundamental para state of N₂ ⁺.     

Time-, wavelength-, and polarization-resolved measurements of OH (A 2Σ+ ) picosecond laser-induced fluorescence in atmospheric- pressure flames

Laser-induced fluorescence of OH (A ²Σ⁺, v’=1) was measured in hydrogen/oxygen and hydrogen/air/nitrogen flames using laser pulses of 80 psec duration. A 2D signal acquisition scheme simultaneously employed wavelength, temporal, and polarization resolution. The signals emitted in different rotational branches exhibit polarization-dependent intensities, depending on the rotational branch of the absorption line used. It is possible to select experimental conditions such that rotational and vibrational relaxation as well as electronic quenching can be monitored simultaneously. Advantages and limitations of the experimental approach are discussed. Numerical simulations are presented of the LIF spectra affected by energy transfer. Received: 29 March 1999 / Revised version: 14 June 1999 / Published online: 27 October 1999     

Femtosecond decay-time measurement of electron-plasma oscillation in nanolithographically designed silver particles

The decay time of the electron-plasma oscillation in silver nanoparticles is measured at a nanoparticle film consisting of regularly arranged, identically shaped and identically oriented particles. By design of a noncentrosymmetric particle shape, SHG in transmission at normal incidence of the fundamental beam is obtained. Therefore the autocorrelation function of the optical near field oscillation of the particle, excited by two emporally overlapping fs laser pulses separated by a defined delay time, could be measured. A decay time of 10¹ fs was extracted. This result shows that the damping of the electron-plasma oscillation in nanometric particles is approximately a factor of 2 larger than expected from the value of the imaginary part of the bulk metal dielectric funtion when consideration of the radiation damping in the particles is included. Received: 28 October 1996/Revised version: 2 December 1996     

Planar laser-induced fluorescence imaging of carbon monoxide using vibrational (infrared) transitions

We report a new imaging diagnostic suitable for measurements of infrared-active molecules, namely infrared planar laser-induced fluorescence (IR PLIF), in which a tunable infrared source is used to excite vibrational transitions in molecules and vibrational fluorescence is collected by an infrared camera. A nanosecond-pulse Nd:YAG-pumped KTP/KTA OPO/OPA system is used to generate 12 mJ of tunable output near 2.35 μm which excites the 2ν band of carbon monoxide (CO); fluorescence resulting from excited CO is collected at 4.7 μm by using an InSb focal plane array. Quantitative, high-SNR PLIF imaging of gas-phase CO is demonstrated at a 10-Hz acquisition rate with a minimum detection limit of 1350 ppm at 300 K. Received: 30 July 1999 / Published online: 16 September 1999     

Infrared-laser-pulse control of bond- and state-selective excitation, dissociation and space quantization: application to a three-dimensional model of HONO2 in the ground electronic state

Selective control over the vibrational excitation and space quantization of the dissociation fragments by optimally designed linearly polarized and shaped infrared (IR) laser pulses of the picosecond (ps) and subpicosecond duration is demonstrated by means of quantum-dynamical simulations within the Schr?dinger wave-function formalism for a three-dimensional (3-D) model of HONO₂ in the ground electronic state, wherein the OH and the ON single-bond stretches are explicitly treated, together with the bending angle between them, on the basis of the ab initio defined 3-D potential-energy surface and dipole function. The high-lying zeroth-order vibrational states of the OH bond are prepared selectively both below and above the dissociation threshold of the ON single bond, and demonstrate a quasi-periodic oscillatory behaviour, manifesting intramolecular vibrational energy redistribution (IVR) on the picosecond timescale. Selective breakage of the ON single bond in HONO₂ with more than 97% probability is demonstrated, along with control of the space quantization of the dissociation fragments: the OH fragments rotating clockwise, OH(c), and anticlockwise, OH(a), are prepared selectively, with the OH(a)/OH(c) branching ratio being as high as 10.975. The results obtained show that optimally designed strong and short IR-laser pulses can compete against IVR and manipulate vibrational excitation and dissociation of polyatomic molecules. Received: 3 November 1999 / Published online: 13 July 2000     

Determination of the rotational temperature and the molecular density in an expanding NH3 jet by infrared absorption

Rotational temperatures are determined by measuring the absorption of infrared laser radiation. The possibilities of this method are critically examined and tested. As a result the molecular density in the expansion could be determined, too. Color-center laser radiation has been absorbed by a molecular jet of NH₃. An anomalous line shape has been observed, related to a Doppler shift from molecules moving along the various streamlines. No deviations from a thermal rotational distribution have been observed.Work supported by Stichting voor Fundamenteel Onderzoek der Materie (F.O.M.)     

Efficient use of the surface plasmon polariton resonance in light scattering from adsorbates

Efficient collection of the scattered light from adsorbates on silver in the attenuated total reflection configuration is demonstrated with a so-called Weierstrass prism. The Raman signal from carbon contamination on silver films is enhanced by two orders of magnitude with respect to the simple external backscattering configuration.     

Characterization of an ethylene free jet

The rotational population distribution in a free molecular jet of ethylene, C₂H₄, is found to be thermal over a range of distances below the nozzle (z/d=0.5–13.2, nozzle diameter d=0.50 mm). Results for on-axis rotational temperature, number density and flow velocity are presented. The average number of gas-kinetic collisions experienced by any molecule in travelling some distance along the jet axis is calculated.     

Dynamics of the CO2 lower laser levels as measured with a tunable diode laser

A tunable diode laser operating in the 4.3 m region is used to probe a conventional cw CO₂ laser discharge. Vibrational populations in the 10⁰0, 02⁰0, 02²0, and 01¹0 levels of CO₂ are measured under lasing conditions, i.e., in the presence of intense 10.4 and 9.4 m fields. The tunable diode laser is also used to monitor the energy transfer processes between the four levels after the passage of an intense 10.4 m pulse. The detailed information provided by the tunable probe laser enables us to determineseparately all the vibration-vibration (V-V) and vibration-translation (V-T) rate constants of importance in the relaxation of the lower laser levels in CO₂. The V-V rate constants are found to vary from a low value of 4.5×10⁴ s^–1 Torr^–1 for the coupling of 01¹0 to 10⁰0 to a high value of 8.0×10⁵ s^–1 Torr^–1 for the coupling of 01¹0 to 02²0.This work was supported by the National Science and Engineering Research Council of Canada and the Provincial Government of Ontario