Pulse duration and collision effects in the multiphoton dissociation of HDCO

Measurements of multiphoton dissociation (MPD) of HDCO gas irradiated by intense CO₂ laser pulses varying in shape and having a duration from 150 ns to ～ 1 μs are reported. It is found that for the same laser pulse energy the short pulses dissociated about an order of magnitude more molecules than the long pulses. Taking into consideration the collision-induced MPD of HDCO previously found, it is shown that to a reasonably good approximation, all the present MPD data for the different pulse durations can be represented on a single, smooth and sharply rising curve of yield versus intensity. This finding is in contrast to the flat intensity response at constant pulse energy found recently for collisionless MPD in SF₆.     

Lifetimes of formaldehyde (A2) in the diffuse region

Lifetimes for the first excited singlet state of H₂CO, D₂CO, and HDCO have been measured from linewidths. In the region of 7000–9000 cm⁻¹ of vibrational energy, lifetimes between 2 and 14 psec were observed. These lifetimes increase with decreasing energy and may be smoothly extrapolated to the results below 4000 cm⁻¹. The H₂CO lifetimes are shorter than D₂CO lifetimes but longer than those for HDCO.     

Isotopically selective IR multiphoton dissociation of 1,3,5-trioxane

Searching for oxygen-isotope selectivity, we investigated the infrared multiphoton dissociation of the formaldehyde trimer around 10 µm, in a range where the molecule has a degenerate and a non-degenerate CO stretch vibration and a degenerate CH₂ deformation vibration. In the region of the two latter, the wavelength dependence of the dissociation yield exhibits sharp structures. They were assigned ton-photon resonances (n = 2, 3, 5) by the help of the IR spectrum in the fundamental and overtone region. The O and C selectivities were very small (1.05) near the non-degenerate CO stretch band, but surprisingly large (2–4) in the CH₂ deformation, which has no isotopic shift. The selectivity is not controlled by the first (n-photon) excitation step, but only by a later step. Its assignment is attempted. The pressure dependence of the dissociation is peculiar: Only after an initial decrease, the yield exhibits the usual rise with pressure. We attribute the decrease to a relaxation which perturbs the two-photon resonance.     

Selective T/H separation by NH3 laser multiple-photon dissociation of CTCL3

The multiple-photon dissociation (MPD) of CTCL₃ and the selectivity of T/H separation were investigated using a pulsed NH₃ laser, whose radiation contained a few lines depending on operating conditions. When Xe was added to chloroform, the dissociation rate of CTCL₃ increased at chloroform pressures below 2 Torr as a consequence of the removal of multiple-photon absorption bottleneck by collisions with Xe. The dissociation rate of CTCl₃ decreased monotonically with increasing chloroform pressure from 0.2 to 7 Torr. The depletion of CHCl₃ was not observed within experimental errors. The lower limit of the tritium enrichment factor in photo-products produced by one pulse irradiation was 570 at chloroform pressure of 2 Torr.     

Fluence and wavelength dependence of the IRMPA and IRMPD of CDCl3 with a CO2 laser

A TEA CO₂ laser was used to study the infrared multiple-photon absorption (IRMPA) and dissociation (IRMPD) spectra of CDCl₃ in the fluence ranges 0.01–1.4 and 7–45 J/cm², respectively, for different sample pressures. Experimental results were modeled with a master equation formulation which includes rotational and anharmonic bottlenecks and collisional effects. Experimental and calculated results show that CDCl₃ has great rotational and anharmonic restrictions at the first stages of excitation. The IRMPD spectrum falls more slowly than the linear absorption spectrum at the blue wing due to intramolecular vibrational relaxation at the quasi-continuum level of excitation.     

Deuterium separation by multiphoton dissociation of dichlorofluoromethane

Absorption and dissociation probabilities of CHCl₂F and CDCl₂F were investigated by a pulsed CO₂ laser in the wavenumber region of largest selectivity for deuterium. The absorption of CHCl₂F, which is a difference band, can largely be suppressed by cooling. At 200 K and at 920 cm^–1 absorption selectivities up to 4000 were found by extrapolation. In the presence of buffer gas, CDCl₂F can be multiphoton excited nearly like a linear absorber (harmonic oscillator). This is interpreted by a nearly resonant collisional relaxation v₇ to v₂ and by the smallness of the cross anharmonicity x₂₇. The dissociation selectivityS was 24,000 at natural abundance. Such large values were measured by a chromatographic method.S depends only onp _D, the partial pressure of the deuterated species. This dependence is approximately ln Sp _D ^–1 . It can be rationalized by considering only the average energy transferred to the nonresonant molecules by collisions with CDCl₂F. The above functional shape is related to an Arrhenius type law. Comparison with trifluoromethane for D separation shows that CHCl₂F has primarily two advantages: its rapid H-D exchange with water and the less stringent requirements of laser energy and pulse length.A preliminary account of this work has appeared in Quantum Electr.2, 13 (1985) (in Chinese)     

Tunable te-CO2 laser-pumped formaldehyde far-infrared lasers: Offsets, assignment, and superfluorescence

Sixty and three absorption transitions in D₂CO and H₂CO, respectively, have produced a number of far infrared laser lines when they are pumped by an etalon-tuned TE-CO₂ laser. Almost all the absorption transitions pumped previously by a free runing TE-CO₂ laser have been efficiently pumped by the etalon tuned CO₂ laser and found to have offset within ±500 MHz from the line-center of the relevant CO₂ pump lines. 22 (1) absorption and 63 (4) emission lines of D₂CO (H₂CO) are assigned. Some of these lines have generated superfluorescence. In paticular, the D₂CO 319-m line pumped by CO₂-9P(32) delivered an output energy of approximately one half that of the well-known D₂O 66-m. It is shown that a large electric dipole moment and an appreciable amount of fractional population in the lower level of the pump transition of this line are responsible to the superfluorescence.     

Infrared multiphoton dissociation of13CF3Cl induced by CO2 laser pulses

Selective infrared multiphoton dissociation of¹³CF₃Cl induced by CO₂ laser pulses adjusted on = 1071.9 cm^–1 has been studied in the energy rangeE between 0.5 and 2 J per laser pulse or fluence range between 5 and 25 J per cm², and in the pressure range between 0.10 and 60 Torr. The effect of these parameters on the isotopic selectivity of the dissociation gives information on the rotational relaxation constants. As for the dissociation probabilities, they vary exponentially withE ^–1. The applicability of such an Arrhenius-type relation is discussed and semi-quantitatively justified.     

Infrared multiple-photon dissociation of CDCl3 induced by a TEA CO2 laser

Infrared multiple-photon dissociation (IRMPD) of CDCl₃ was studied using a tunable TEA CO₂ laser. Effects of number of irradiation pulses, wavelength and energy fluence as well as of sample pressure on the reaction yield are reported.     

Observations on the spectral dependence andT/D isotope selectivity in the CO2 laser multiple-photon dissociation of trifluoromethane

Pulsed CO₂ laser multiple-photon dissociation of CTF₃ (v ₂ mode) bathed in argon and CDF₃, CHF₃ or CCl₄ is examined as a function of laser wavelength (9.2–9.6 m) and fluence. The dependence of the dissociation profile on wavelength is analyzed and comparisons are made to prior work. The single-stepT/D enrichment factor for infrared photolysis of trifluoromethane is measured; potential practical isotope separation is discussed. Pulsed infrared laser photolysis of CTF₃ (v ₅ mode) using a 12 m NH₃ laser is also attempted.     

Deuteron quadrupole coupling in formaldehyde

The hyperfine structure of the 1₁₀-1₁₁ rotational transition of D₂CO has been observed with a beam-maser spectrometer and the spin-rotation and electric quadrupole coupling constants have been determined. Using previously reported measurements on HDCO, the complete electric field gradient tensor at the position of the deuteron has been evaluated.     

Pulsed optoacoustic detection of multiple photon excitation in molecules

Multiple photon excitation, saturation, and linear absorption of SF₆-argon mixtures when irradiated by a high power CO₂ TEA laser is investigated using a pulsed optoacoustic technique. At low intensities the expected linear dependence of the absorption on laser intensity is observed. At intermediate intensities the absorption exhibits a square root dependence on the incident laser intensity, a dependence which is typical for saturation of an inhomogeneously broadened absorption. At even higher intensities, the absorption shows an intensity dependence typical of multiple photon excitation. The laser intensity was varied between 0.016 kW/cm² and 5 MW/cm², values lower than that needed to produce multiple photon dissociation of SF₆. Increasing the collision frequency of the absorbing molecules with an inert buffer gas is observed to quench the multiple photon excitation.     

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     

Pulsed-laser photolysis of Mn2(CO)10: A time-resolved fluorescence study

Mn₂(CO)₁₀ was photolysed in the gas phase by the XeCl-excimer laser with fluence in the range 25–300 mJ/cm² and a dye laser. The UV/VIS emission of the products was probed on a nanosecond time scale. The emission from excited states of metal atoms was detected only. The Mn atoms are predominantly formed in their ground statea ⁶ S _{2 1/2}. The absorption of one photon and the subsequent relaxation process leads to the formation ofz ⁶ P _J ⁰ (J = 11/2, 21/2, 31/2) states and emission of photons at a wavelength of 403 nm. The formation of the excited statese ⁸ D _{5 1/2},z ⁶ F _{4 1/2} ⁰ ande ⁶ D _{4 1/2} and the subsequent emission observed at wavelengths of 357, 383 and 446 nm requires the absorption of two photons by the ground-state Mn atoms. In addition, transition from thea ⁶ D _j (J = 11/2, 21/2) lower states were observed in the wavelength-resolved Laser-Induced Fluorescence (LIF) spectra.     

VPT2+K spectroscopic constants and matrix elements of the transformed vibrational Hamiltonian of a polyatomic molecule with resonances using Van Vleck perturbation theory

Vibrational levels of polyatomic molecules are analysed with Van Vleck perturbation theory to connect experimental energy levels to computed molecular potential energy surfaces. Vibrational matrix elements are calculated from a quartic potential function via second-order Van Vleck perturbation theory, a procedure that treats both weak and strong interactions among vibrational states by approximately block-diagonalising the vibrational Hamiltonian. A clear and complete derivation of anharmonic and resonance constants as well as general expressions for both on- and off-diagonal matrix elements of the transformed Hamiltonian is presented. The equations are written in partial fraction form and as a constant multiplied by a harmonic oscillator matrix element to facilitate removing the effect of strongly interacting resonant states both in analytical formulae and in computer code. The derived equations are validated numerically, and results for the isotopomers of formaldehyde (H₂CO, HDCO, D₂CO) are included. The implications of the equations on zero-point energy calculations and experimental fits are discussed. The VPT2+K method is defined by these results for use in fitting and calculating vibrational energy levels.     

The A2 (n, 3px) Rydberg state of formaldehyde

Pairs of bands were observed in the absorption spectrum of H₂CO, HDCO, and D₂CO in the 1470-1430 Å region which were characterized by well-defined rotational band contours. A band contour synthesis of the observed band envelopes demonstrated that the bands are described by type C selection rules. From the observed intervals and their shifts on deuterium isotope substitution these bands were assigned to quantum additions of ν₅ and ν₆. The symmetry of the upper state was deduced to be ¹A₂ from the vibrational assignment of the bands and their polarizations, while the results from MO theory lead to the orbital assignment n → 3p_x. The electronic transition then is .     

Effect of gas pressure and pulse length on the isotopically selective multiphoton dissociation of CF3Cl under CO2 laser pulses

The multiphoton dissociation of CF₃Cl induced by TEA-CO₂ laser pulses has been studied in a focused beam geometry. TheR(10) [00°1–02°0] ( ) laser line was used, so as to dissociate preferentially the minor isotopic component¹³CF₃Cl. The isotopic selectivityS and the dissociation probability per pulse ω were measured in the pressure range between 0.25 and 8 Torr. With short laser pulses (90 ns FWHM),S is found to increase slightly with gas pressure up to 2 Torr, and ω, to increase almost linearly over the whole pressure range studied. A schematic model is proposed which satisfactorily explains these results if the transition rates across the energy level spectrum of the CF₃Cl molecules are assumed to increase with gas pressure.     

Rotationally resolved infrared-ultraviolet double resonance spectroscopy in molecular D2CO and HDCO

Rotationally resolved infrared-ultraviolet double resonance (IRUVDR), consisting of sequentially excited rovibrational and rovibronic transitions sharing a common intermediate molecular level, is demonstrated. The technique employs pulsed CO₂ and tunable dye lasers and is applied to the molecules D₂CO and HDCO. For D₂CO, infrared pumping produces 100fold population enhancement in specific rotational sublevels of the v₄ = 1 level of the $\text{X}\text{?}{}^1\text{A}{}_1$ electronic ground state, followed by ultraviolet excitation in the 365-nm 4₁⁰ band of the $\text{A}\text{?}{}^1\text{A}{}_2\text{←}\text{X}\text{?}{}^1\text{A}{}_1$ electronic system. This ultraviolet excitation occurs at a specific set of dye laser frequencies, determined by the preceding rovibrational transition, and is detected by molecular fluorescence in the visible region. Similar effects observed in HDCO involve rovibrational pumping to either the v₆ = 1 or v₅ = 1 levels and give rise to enhanced rovibronic transitions in the 6₁⁰ and 5₁⁰ bands of the $\text{A}\text{?}\text{←}\text{X}\text{?}$ system, respectively. The resulting IRUVDR spectra enable detailed spectroscopic assignments to be made and are consistent with previous results from infrared and ultraviolet absorption, laser Stark, and infrared-radiofrequency double resonance spectroscopy. Collision-induced satellite structure, arising from rotational relaxation of the intermediate rovibrational level in the IRUVDR sequence, is also reported.     

红外激光场诱发下的多原子分子离解反应模型

本文在以前工作的基础上,继续讨论了多原子分子在红外激光场作用下产生多光子离解的机制,得到了分子各个振动模之间的非线性耦合方程组,以SF₆分子为例,数值计算了模-模间的能量转移时间、费密共振作用、各个模被激光场激发的程度,最后联系到单分子反应的模型,讨论了多原子分子的离解速率,基本上得到了与实验现象一致的结果。 关键词：     

Nitrogen related excitation processes in a mercury bromide laser discharge

The role of nitrogen as a buffer gas constituent in an avalance discharge mercury bromide laser has been examined, and it is shown that a change over in excitation from electron impact dissociation of HgBr₂ to energy transfer dissociation by excited nitrogen occurs at 1.5%N ₂. This is explanable in terms of excitation cross-sections if considerable pumping occurs from excited states of nitrogen which are higher in energy than the metastableA state. When excitation via nitrogen is dominant, a high dischargeE/N value is needed to avoid coupling of energy to unwanted vibrational excitation.