IR multiple-photon dissociation by a focused uniform beam

An improved analytical method is presented in which the reaction yield in the IR multiple-photon dissociation by a focused uniform beam is expressed in a generalized form as a function of fluence. The analytical solution is derived for a real focusing geometry by assuming the cumulative log-normal distribution (CLND) for the functional form of the dissociation probability vs. fluence. Also presented is a shortcut analytical method with simple and convenient algebraic expressions which approximate the exact analytical solution, thereby speeding up the analysis of experimental data.     

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.     

Towards an explanation of collisionless multiple-photon laser dissociation of SF6

The rapidity and high degree of molecular vibrational excitation by the absorption of ir laser light in SF₆ and other molecules may be due in large part to the anharmonic splitting of excited vibrational states. Anharmonic splitting of an overtone or combination vibrational level (i) is possible only in molecules with degenerate vibrational states, (ii) can be comparable in magnitude to the net anharmonic shift of the level, (iii) is generally much larger than the rotational shifts which have previously been proposed as an explanation for the dissociation of SF₆. We find that consecutive nearly resonant transitions are possible in SF₆ up to υ₃ = 5 to 10.     

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.     

Experimental selection of molecules for isotope separation by multiple-photon dissociation in an intense IR field

Consideration is given to selectivity estimation methods during polyatomic molecules dissociation by multiple photon absorption. Taking the CH₃NO₂ molecule as an example, the possibilities of selectivity estimations made on the electron-excited dissociation products (luminescence) are shown, as well as on the measurements of the energy absorbed in a strong IR field being transformed into heat. Some advantages of the last method of the selectivity estimation are discussed. The experiments on nitrogen-isotopes separation in the mixture of CH₃ ¹⁴NO₂ and CH₃ ¹⁵NO₂ molecules are carried out when exciting thev ₇ vibration with the isotope shift of about 7 cm⁻¹ and thev ₁₃ vibration with no isotope shift in the linear absorption spectrum. The contribution of secondary chemical reactions to the separation process is discussed.     

Infrared multiphoton dissociation of vinyltrifluorosilane

Infrared multiphoton absorption and dissociation of vinyltrifluorosilane molecules under the action of pulsed TEA CO₂-laser were experimentally studied. The composition of the end dissociation products has been analyzed. Using quantum chemical calculations, we have identified the dissociation pathways that lead to the observed end products. Transition state geometries, enthalpies and activation energies for the dissociation pathways have been calculated. The dissociation channel ratio was determined under used experimental conditions. The silicon isotope selective infrared multiphoton dissociation has been performed at different wavelengths of the CO₂-laser radiation. PACS 82.50Bc; 82.30Lp; 31.15.Ew     

Infrared multiphoton dissociation of difluorosilane

Infrared (IR) multiphoton absorption and dissociation of difluorosilane molecules under the action of a pulsed transversely excited atmospheric CO₂ laser were experimentally studied. It has been found that the multiphoton absorption is strongly saturated due to the rotational bottleneck effect. Isotope-selective IR multiphoton dissociation of difluorosilane was performed at 977.2 cm^-1. The dissociation rate for ²⁸SiH₂F₂ isotopomer has been found to be about twice as high as for the other isotopomers at this wavelength. PACS 82.50.Bc; 82.30.Lp     

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.     

Infrared laser multiple photon dissociation of thiophene in gas phase

Infrared laser multiple photon excitation/dissociation of Thiophene (Th) was studied as a function of Th pressure, laser pulse energy, pulse duration and added buffer gas. While the excitation process was probed via optoacoustic technique, the stable reaction products were analyzed by IR spectroscopy and mass spectrometry. Although C₂H₂ and CH₃CCH were the major hydrocarbon products under all experimental conditions, the distribution of these, as well as higher hydrocarbons of lower yield, was found to be very much dependent upon the experimental conditions. The laser induced reaction under dielectric breakdown conditions with either high substrate pressure or laser energy produced significant amount of CS₂ and unidentified polymer as well. We propose a mechanism involving breakage of the C–S bond in Th to form an unstable 1,5-diradical which further decomposed via different channels. However, at higher substrate pressures, radical-Th reactions complicated the overall chemistry of the system. Evidences for collisional energy-pooling and rotational hole-filling were also obtained.     

Electron-impact dissociation and transient properties of a stored LiH2 - beam

The fragmentation of LiH₂ ^- anions after electron impact was investigated at the heavy-ion storage ring TSR. The main reaction channel was found to be electron detachment followed by a breakup into LiH + H. In the first ms after production of the molecular ions in a cesium sputtering ion source, additional contributions were observed in the Li + H₂ and Li^- + H₂ channels, hinting at an initial population of a short-lived state of the anion. To gain a better understanding of the mechanisms underlying the observed behavior of the system, ab initio calculations of relevant potential energy surfaces were performed at selected geometries. The experimental findings are discussed in the light of these calculations.     

Characteristics of multiple-photon dissociation of OsO4 molecule by two frequency tunable CO2-laser pulses

Using two-frequency technique for the multiple photon dissociation of OsO₄ molecule by IR laser radiation, the following new results have been obtained: 1. the narrow resonances of multiple photon absorption on few low lying vibrational transitions have been found in the dissociation yield as a function of exciting frequency ν₁; 2. the structure of the dissociation yield as a function of dissociating frequency ν₂ connected with high lying vibrational transition has been studied; 3. the kinetic of the vibration relaxation of high vibrationally excited molecules was investigated; 4. the unimolecular character of the multiple photon dissociation of OsO₄ has been proved.     

Raman spectroscopy of infrared multiple-photon excited molecules

The method of spectroscopy of spontaneous Raman scattering (RS) with time resolution has been applied for the first time to diagnose the process of multiphoton ir molecular excitation (MPE). Some aspects of RS diagnostics of MPE processes are being analyzed. It has been shown experimentally on SF₆ and CF₃I molecules that it is possible to study such important characteristics of excitation process as the fraction of molecules involved in the process of excitation, vibrational energy distribution of molecules, stochastization of inner molecular energy.     

多光子激发相干态的Wigner函数

Wigner函数的负性是非经典量子态的重要判据之一.利用Fock态表象下Wigner函数的一般表达式,重构了相干态｜z〉的k光子激发态｜+k,z〉～a^－k｜z〉（k≥1）的Wigner函数,并根据其数值结果讨论了该量子态的非经典特性（这里a^－1为Bose湮没算符的逆算符,其作用相当于Bose产生算符）.结果表明,不论k取奇数还是偶数,相干态的这些k光子激发态都具有非经典特性;而且k的取值越大,这些量子态的非经典特性越明显. 关键词： 非经典量子态 激发相干态 Wigner函数 非经典特性     

Infrared multiple photon dissociation spectroscopy of transition metal oxide cluster cations

Infrared spectra in the range of 530–1400 cm^–1 are presented for tantalum oxide cluster cations (x = 3, 4 and 6). These spectra are obtained via multiple photon dissociation (MPD) spectroscopy of free cluster cations moving in a molecular beam. The IR spectra for are compared to spectra of as well as to the experimental data available for vanadium oxide cluster cations from IR-MPD spectroscopy. For and the IR spectra exhibit very strong similarities (including the band positions), whereas absorption bands in are relatively blue-shifted by about 20–40 cm^–1.     

Raman study of ion-molecules interaction in poly(methylmetacrylate)-based gel electrolytes

Gel electrolytes have been obtained, containing LiX (X=ClO₄, N(CF₃SO)₂, AsF₆) dissolved in a ethylene carbonate-propylene carbonate mixture and PMMA as polymeric matrix. Ionic conductivity has been measured, for two different lithium salts. The changes in the Raman spectra have been studied as a function of the polymer content, lithium salt concentrations and for different anions. Two satellite bands of the internal bending and stretching modes of ethylene carbonate appear in the spectrum of lithium containing samples, because of the cation-solvent molecule interaction. Paper presented at the 1st Euroconference on Solid State Ionics held in Zakynthos, Greece, Sept. 11–18, 1994     

Direct measurement of lifetimes of infrared multiple-photon dissociated molecules

A beam of mass selected SF ₅ ⁺ ions is crossed with a pulsed CO₂ laser beam. The distribution of lifetimes of infrared multiple-photon pumped SF ₅ ⁺ ion-molecules prior to dissociation into SF ₄ ⁺ +F has been measured directly using a time-of-flight ion-beam technique. The data provide new information on the distribution of the total internal energy of molecules excited by absorption of infrared radiation.     

Resonance-enhanced multiple-photon ionisation spectroscopy of excited sulphur atoms

Sulfur atoms are produced in the excited 3s ²3p ^{4 1} D ₂ and 3s ²3p ^{4 1} S ₀ levels by two-photon photodissociation of CS₂ in the gas phase in the region 285–305 nm. These excited atoms are detected by three-photon (two to resonance) ionisation at selected laser wavelengths. Many new transitions have been observed which have not been reported previously. The new dark states that have been accessed by two-photon absorption have been characterised and the energy levels with respect to the ground ³ P ₂ state have been determined. Configuration interaction between 6p ³ P ₁, 6p ⁵ P ₁, and 4p¹ P ₁ states, and also between 6p ³ P ₂, 6p ⁵ P ₂, and 4p¹ D ₂ states has been observed. It is found that intermediate states reached from the ¹ S ₀ level through two-photon absorption lie above the first ionisation potential of S⁺(⁴ S ⁰). It is proposed that autoionisation into the ⁴ S ⁰+e^– continuum is a dominant mechanism in the decay of these levels, although ionisation by a further photon absorption is not ruled out.