Sub-Doppler excited molecule energy transfer spectroscopy

A sub-Doppler spectroscopic technique involving the detection of vibrational energy transfer in excited molecules with selected velocity components at a microphone diaphragm is demonstrated. The technique is applied to the investigation of thev ₃ R(16) transition in HCN and the results compared with a previously derived theoretical model.     

Theory of intracavity absorption spectroscopy with a singly resonant optical parametric oscillator

The suitability of a singly resonant optical parametric oscillator pumped by a one-mode field and oscillating simultaneously in several signal and idler modes, for intracavity absorption spectroscopic measurements is studied theoretically. For steadystate operation, the enhancement factor ξ indicating the increased detection sensitivity, is shown to be mainly determined by the ratio of the intensity in one of the signal modes to the intensity (per mode) due to parametric fluorescence. Hence, rather high values of ξ, say of order 10⁸ or more, might be attainable, at least in principle. For pulsed operation, on the other hand, a numerical analysis leads to the result that for realistic pulse durations only moderate values of ξ (smaller than some 10³) will be found. Paper given in parts at the 6th Vavilov-Conference on Nonlinear Optics, Novosibirsk, USSR, 1979.     

A differential technique to measure small product yield increments in a time-of-flight mass spectrometer for investigating IR spectra of highly excited polyatomics

We present an experimental technique for measuring small product yield increments in a specially designed time-of-flight mass spectrometer with a supersonic jet. Advantages of this technique are demonstrated in measuring the photodissociation IR spectrum (990–1050 cm^–1) of CF₃I molecules with vibrational energy at the threshold value. The differential technique has enabled us to reveal an anomalously narrow width of the spike of thev ₁ band of CF₃I. We discuss this anomaly.     

New results on ultrafast coherent excitation of molecular vibrations in liquids

Coherent Raman probe scattering experiments are performed to study dynamical processes of polyatomic liquids at 300 K. For single homogeneous transitions the dephasing timeT ₂ is readily obtained from time resolved investigations. Spectral studies show an interesting time dependent shift in scattered frequency. After the excitaiton the vibrating molecules are shown to relax freely with their resonance frequency. Multiple, equally spaced transitions exhibit a beating phenomenon which provides the dephasing time and the frequency interval between neighboring vibrational states. Inhomogeneously broadened systems do not allow a ready determination of the dephasing time by the present probing technique. Previous experiments on the subject have to be reconsidered.     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

Light-polarization modifications in a multipass cavity

This paper analyses the slight change undergone by the polarization of a laser beam performing a multipass between two spherical mirrors facing each other. We replace the general 16-parameter Mueller formalism by an approximate 7-parameter one, and we give a quantitative experimental criterion for the validity of this approximation. Then we apply this formalism to the analysis of our experimental data. The results evidence:i) intrinsic birefringence in the mirror coatings (typical value per reflexion 2 to 4×10^–4 rad);ii) birefringence due to off-normal incidence (typically 3.6×10^–5 rad per reflexion for an incidence of 2×10^–2 rad);iii) optical rotation, of purely geometrical origin (typically 14° for a multipass with revolution symmetry and 100 forward-backward passes under constant incidencei=2°);iv) no observable circular dichroism (10^–6). Finally these results are discussed in connection with possible associated systematics in a parity violation experiment which motivated this work.Associé au C.N.R.S.     

Energy transfer processes in two different bifluorophoric laser dyes

The mechanism of intramolecular energy transfer in two bifluorophoric laser dyes has been investigated by measurements of laser parameters, excited state absorption and phosphorescence spectra. The new value found for the dimethyl-POPOP triplet energy (48.0 kcal/mole) accounts for the different behaviour of the two classes of bifluorophoric dyes used in this investigation.     

Planar laser-fluorescence imaging of combustion gases

An overview is provided of the planar laser-induced fluorescence (PLIF) method, which currently allows simultaneous combustion measurements at more than 10⁵ flowfield points. Important advantages of the method include its relatively high signal strength, ease of interpretation, and applicability for determining several flowfield variables (including concentration, temperature, velocity, pressure and density). Example results are shown for a turbulent non-premixed flame, a spray flame, a rod-stabilized premixed flame, and a diffusion flame from a fuel jet in cross-flow.     

Dynamic absorption effects in KrF* amplifiers

The results of transient loss measurements performed in a self-sustained discharge KrF^* amplifier are reported. Analysis of these results gives a minimum value of 20 for the effective gain to loss ratiog ₀/_eff, indicating that efficient extraction of energy in subpicosecond KrF^* amplifiers in the 1 J range should be achievable.     

New TEA-lasers based onD′→A′ transitions in halogen monofluoride compounds: ClF (284.4 nm), BrF (354.5 nm), IF (490.8 nm)

As an outcome of a systematic study of excitation kinetics and fluorescence spectra concerning theD′(3π_2u )→A′(3π_2g ) transitions in homonuclear diatomic halogens and corresponding transitions in interhalogen molecules [1], this paper describes, for the first time, TEA laser action in the three halogen monofluorides ClF, BrF, and IF. Output energies in the mJ range were demonstrated in a fast TEA discharge arrangement at the wavelengths of 284.4, 354.5, and 490.8 nm for ClF, BrF, and IF, respectively. The results suggest parameter scalability and wavelength tunability.     

Investigation of UV-laser induced metallization: Platinum from Pt (PF3)4

We have measured the Pt deposition yields on various substrate materials from Pt(PF₃)₄ in the case where a KrF laser irradiates the solid surface. The data imply that an ample amount of electrons is produced by the laser surface interaction and dissociative electron capture initiates the metal deposition. The metal atom release is completed by a concerted surface reaction at a reduced energy demand. This is evidenced by thermochemical considerations. A simple criterion is derived to estimate the attainable spatial resolution. Sudden melting and evaporation beyond a certain layer thickness interferes with the deposition process. This is in accord to a model given, based on a poor thermal contact at the platinum substrate interface. The results may help to optimize uv laser induced metal deposition with respect to purity, adherence and structure.     

The identification of nonlinear molecular systems by spectroscopic methods

The Wiener functional expansion method for the analysis of nonlinear systems is applied to identify and analyze both nonlinear and linear molecular systems by spectroscopic methods. As the sampling filter (monochromator) of any spectroscopic apparatus may be defined by a Weber-Hermite polynomial, an analysis of the refracted or scattered light by orthogonal polynomials is easily achieved. Time averaging obtains the Weber-Hermite coefficients which permit the characterization of the molecular system with respect to the polarization of the incident and scattered light. In the case of two series of measurements made with incident and emerging light polarized in different directions: the identification of the JonesM matrices for the molecular system irradiated is possible. In the case of three series of measurements made, for example, with incident and emerging light (a) circularly polarized corotating, (b) circularly polarized contrarotating, and (c) plane polarized perpendicular: the identification of the molecular system's McClain invariants related to the vibrational symmetry group for Raman inelastic light scattering is possible. The analysis presents a unified picture of elastic and inelastic light scattering and one-photon and two-photon processes. The apparatus described would detect those instances in molecular systems for which Beer's law does not apply.     

Doppler-free resonant two-photon transition for isotope separation

The Doppler-free two-photon transition by the use of two opposing laser beams makes the highly selective excitation of isotopic molecules possible. Saturation and pressure dependence of Doppler-free two-photon excitation with arbitrary amplitudes of the optical fields have been calculated and compared with those of the two-step transition and the single-photon transition. The result at the Doppler limit for low pressure gas reveals that the probability of the selective two-photon excitation with a moderate laser power can be larger than that of the single-photon excitation as well as that of the two-step excitation.     

The influence of phase-modulation on femtosecond time-resolved coherent Raman spectroscopy

The influence of phase-modulation on femtosecond time-resolved coherent Raman scattering is investigated theoretically and experimentally. The coherent Raman signal taken as a function of the spectral position shows unexpected temporal oscillations close to time zero. A theoretical analysis of the coherent Raman scattering process indicates that the femtosecond light pulses are amplitude and phase modulated. The pulses are asymmetric in time with more slowly decaying trailing wings. The phase of the pulse amplitude contains quadratic and higher-order contributions.     

Multiphoton absorption and luminescence of osmium tetroxide

Both the multiphoton absorption and the luminescence brightness of osmium tetroxide induced by absorption of temporally smooth CO₂ 10P(20) laser pulses of 10 and 40 ns FWHM have been measured for pressures in the range 6.7 to 200 Pa. A dependence of these phenomena on laser pulse length is observed. Comparison of the luminescence brightness to the average excitation shows that the distribution of the multiphoton excitation depends on the laser pulse intensity for the two pulse lengths studied.Issued as AECL Contribution No. 8806