Threshold dependence of the vibrational excitation of molecules on laser radiation intensity

The collisionless vibrational excitation of a polyatomic molecule in an IR laser radiation field has been theoretically studied. It has been shown that (i) the degree of vibrational excitation (namely, number 0000 of vibrational quanta of a molecular mode near-resonant with the IR laser field that are absorbed by the molecule) is low if laser pulse intensity P (energy flux density in the laser beam) is lower than a certain critical value P _cr; (ii) the degree of excitation abruptly increases after crossing the boundary where P = P _cr; (iii) this effect is attributed to two properties inherent in polyatomic molecules, namely, the anharmonicity of the vibrational mode interacting with the laser field and the energy exchange with other modes; and (iv) at P > P _cr, number 00000 is determined only by energy density Φ = Pτ_P, where τ_P is the laser pulse duration, 00000 monotonically increases with increasing Φ. The model is in good agreement with the experimental data.     

Intermolecular vibrational relaxation upon multiphoton excitation of triplet molecules by a CO2 laser

Intermolecular vibrational relaxation is studied in mixtures of polyatomic molecules (benzophenone and fluorene) with bath gases after multiphoton excitation of the triplet molecules by CO₂ laser radiation. The dependences of the decay rate and the intensity of laser-induced delayed fluorescence on the laser energy density E _CO2 and pressure P _fg of bath gases are analyzed. They are found to be different for the fast and slow components of delayed fluorescence, which decays nonexponentially. It is shown that a change in the decay rate of the fast fluorescence component with increasing pressure P _fg is governed by the properties of vibration-translation relaxation. The efficiency β of this process is estimated in a broad range of vibrational energies. It is found that β weakly changes with increasing E _vib upon excitation of molecules to high vibrational levels. The features of intermolecular vibrational relaxation at high densities of anharmonically coupled vibrational states are discussed.     

Relaxation Processes at High Levels of Vibrational Excitation of Polyatomic Molecules in the Ground Electronic State

By the spectral and kinetic characteristics of the luminescence of vapors of polyatomic molecules (anthracene, anthraquinone, fluorenone) initiated by selective IR multiphoton excitation (IR MPE) of molecules in the ground electronic state S ₀ the relaxation processes proceeding under vibrational excitation of molecules to energies exceeding the energies of the lower excited electronic states have been investigated. The changes in the spectral and kinetic characteristics with increasing CO₂ laser energy density and vapor P _v and foreign gas pressure P _FG are analyzed. They are similar to the characteristics obtained for normal fluorescence of these molecules with changing vibrational energy E _vib content. On the basis of experimental data and model calculations it has been concluded that at the laser radiation densities used in the case of IR MPE the molecules reach energies considerably exceeding the energies of the electronic levels. It is shown that a nonadiabatic connection between the electronic states leads to the population of mixed electronic states isoenergetic to the vibrational levels of the ground electronic state and to emission of delayed luminescence spectrally identical to the normal luminescence of these molecules. It has been found that when high vibrational levels are populated, new relaxation channels, such as reverse electron relaxation, emission from high vibrational levels of the ground electronic state, and multiquantum vibrational energy transfer at collisions leading to a rapid establishment of vibrational equilibrium become important.     

Observation of resonance electronic and non‐resonance‐enhanced vibrational natural Raman optical activity

Natural resonance electronic Raman optical activity (ROA) is observed for the first time. Coincidently, the first example of vibrational ROA enhanced by low‐lying electronic transition is reported. These new phenomena were measured using the rare‐earth complex Eu(tfc)₃ (+)‐tris[3‐trifluoroacetyl‐D ‐camphorato]europium(III), where electronic resonance occurs between the 532‐nm laser excitation and the ⁷F₁ → ⁵D₁ transition of the Eu³⁺ metal center. Electronic Raman spectra involve the Raman transitions terminating on the low‐lying electronic states of Eu(tfc)₃. The observed vibrational ROA spectra are enhanced relative to typical ROA spectra by the proximity of vibrational states of Eu(tfc)₃ to its low‐lying electronic states with significant magnetic‐dipole character, whereas the parent vibrational Raman spectra do not appear to be resonance‐enhanced since the 532‐nm vibrational Raman spectrum has similar relative intensities to the corresponding Raman spectrum measured with 1064‐nm laser excitation. Copyright © 2010 John Wiley & Sons, Ltd.     

Interhalogen UV laser on the 285 nm band of ClF

A new UV-laser operating on the 285 nm band of ClF is reported. Fluorescence and laser oscillation on numerous vibrational and rotational lines has been observed following e-beam excitation of a Ne/F₂/Cl₂ mixture. The upper laser level is probably formed in an ion recombination reaction of fluorine and chlorine ions.     

强红外场作用下BCl3振动态传能动力学研究

基于文献[1],本工作在较高泵浦激光能通量范围,测量并研究了BCl₃分子振动激发v_3吸收谱及时间演变,观察了v₃激发弛豫的几种能量转移过程,以及对泵浦激光能量BCl₃气压等参数的依赖关系。表明泵浦光脉冲产生一个振动态非热分布的系综,转动能量转移对引起这种非热分布有重要作用。用简化碰撞动力学模型讨论了BCl₃振动激发吸收谱的演变过程,得到振动态再分布的简单关系;Pτ_v-v≌c/K′(T_v,T₀,q)和等效振动温度、平均吸收光子数的分析表达式,与实验结果定性地符合。 关键词：     

Direct observation of the vibrational energy redistribution in (CF<Subscript>3</Subscript>)<Subscript>2</Subscript>CCO molecules resonantly excited by femtosecond infrared laser radiation

The dynamics of multiphoton excitation of (CF₃)₂CCO molecules has been investigated under the condition of resonant action of femtosecond infrared laser radiation on the ν₁ vibrational mode of the C=C=O bond. It has been shown that the mode-selective excitation of this vibration occurs up to the ν = 6 level. The kinetics of the subsequent intramolecular vibrational energy redistribution from the ν₁ mode has been measured. A value of 5 ± 0.3 ps has been obtained for the characteristic time of this process.     

Fluorescence spectrum of chlorine dioxide induced by the 4765 Å argon-ion laser line

The fluorescence spectrum induced in ClO₂ by excitation with the 4765 Å argon-ion laser line has been studied under moderate resolution with the laser in single mode operation and under high resolution with the laser in multimode operation. The most intense features of the fluorescence have been assigned to excitation by the 23_{2, 22} ← 24_{2, 23} transition of the (0, 0, 0) ← (0, 0, 0) band of ³⁷ClO₂. Another set of features has been assigned to excitation by the 38_{0, 38} ← 37_{0, 37} transition of the (0, 0, 0) ← (0, 0, 0) band of ³⁷ClO₂.The vibrational structure and the ν₁ vibrational dependence of the rotational structure in the fluorescence have been least squares fitted giving a new set of vibrational constants and vibration-rotation interaction constants, $\text{α}{}_1{}^{\mathrm{B}}$ and $\text{α}{}_1{}^{\mathrm{C}}$.     

Three-phonon stimulated Raman scattering in an orthorhombic LuAlO<Subscript>3</Subscript> crystal

High-order stimulated Raman scattering (SRS) has been revealed in a LuAlO₃ crystal upon stationary picosecond laser excitation. All recorded Stokes and anti-Stokes χ⁽³⁾-nonlinear laser components are attributed to three SRS-promoting А _g vibrational modes of its octahedral anionic units (AlO₃)^–3.     

Strong selective excitation of Raman-active vibrations and energy transfer between low-lying vibrational states of a CO2 molecule studied by PARS and CARS

We experimentally demonstrate the novel technique of inducing the highly nonequilibrium distribution of molecules over vibrational states by two-frequency coherent Raman excitation. The technique can be used for selective excitation of totally symmetric and other Raman-active molecular transitions. Two counter propagating focused laser beams (second harmonic of Nd: YAG and dye laser) were used to induce population difference changes at the 00⁰0–10⁰0 transition in CO₂ molecules. The excitation and relaxation kinetics of this and neighbours vibrational modes of CO₂ were studied both by CARS and PARS. Vibrational excitation of up to 20% of the total number of irradiated molecules is measured; previously unknown desactivation constant of CO₂ (10⁰0) and CO₂ (02⁰0) states via CO₂ (01¹0) state is estimated to be K = (3±1) × 1 ⁵s^-1torr^-1.     

低能电子与氢分子碰撞的振动激发积分散射截面的研究

采用振动密耦合方法,研究了低能电子与H₂分子碰撞的振动激发积分散射截面.研究表明,使用18个Morse振动波函数、5个分波和4个对称性可以得到收敛的0→0,0→1,0→2和0→3积分散射截面;而且振动波函数的性质和振动能级的精确性会直接影响振动激发散射势能和振动激发积分散射截面.计算结果与实验符合得很好. 关键词： 电子散射 振动激发 2分子')" href="#">H₂分子 积分截面     

Theoretical study of the time-resolved photoelectron spectrum of Na 2F: effects of thermal initial conditions

The excited state dynamics of the Na₂F cluster initiated by a femtosecond laser pulse is studied considering a thermally excited initial sample. Within a pump-probe set-up, the time-dependent photoelectron spectrum is calculated, which is shown to be a sensitive tool to study intramolecular motion of the cluster. Temperature effects are taken into account through thermal averaging over the time-dependent spectra obtained from different initial vibrational states of the cluster. The nuclear motion upon laser excitation is described by full-dimensional quantum wavepacket propagation using explicit, realistic pump and probe pulses. The characteristic features of the time-resolved photoelectron spectra of the Na₂F cluster, identified as due to periodic bending motion of the cluster as well as to the excitation of the stretching mode, are found to be robust against increasing vibrational temperature of the cluster beam. This finding is important for possible future experiments.     

HF Laser Based on Thermal- and Photon-Branched Chain Reactions Initiated by IR Laser Radiation

A chemical H₂–F₂ laser (oscillator and amplifier) initiated by means of IR radiative excitation of vibrational levels of HF molecules is studied under the conditions of development of a thermal-branched chain reaction caused by thermal dissociation of gaseous additions to the laser mixture. It is shown that, using F₂SO₃ addition at a partial pressure of 40 Torr, an H₂–F₂ laser with a mixture pressure of 1~bar initiated by a pulsed hydrogen fluorine laser can provide an output exceeding 120–200 J/liter in 20–50 ns laser pulses.     

Femtosecond laser control of intramolecular vibrations in a liquid

Optical control of coherent intramolecular oscillations in chloroform CHCl₃ and dimethyl sulfoxide (CH₃)₂SO is attained experimentally under normal conditions by means of femtosecond polarization spectroscopy. Nonresonant excitation of the medium is accomplished by a sequence of two linearly polarized laser pulses. The state of the medium is probed by the third pulse via the optical Kerr effect. We show that control over the vibrational dynamics of molecules on a sub-picosecond scale can be achieved by varying the delay between the excitation pulses and their relative intensity.     

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.     

Kinetic modelling of electrooptically Q-switched CO2 laser

In this paper, a six-temperature model for CO₂ lasers is used to describe the process of the dynamic emission in the electrooptically Q-switched laser. The dissociation of CO₂ molecules, the electron excitation and the energy-transfer of vibrational levels and the rotational relaxation of rotational levels are involved. The calculated pulse waveforms are in good agreement with the experiment.     

Slow intermolecular redistribution of vibrational energy in SF6 gas excited by a tea CO2 laser

Infra-red fluorescence (IRF) spectra of SF₆ excited by the 944.2 cm^-1 line of a pulsed CO₂ laser were observed at various times after the time of the laser excitation. Each spectrum showed a strong IRF peak of the v₃ mode which was red shifted relative to the room temperature fundamental (948 cm^-1) by an amount which depended, apart from the level of excitation, on the different times employed. For a strong excitation with 〈n〉 ≈ 11 photons absorbed per molecule, a significant decrease of red shift versus time was observed, indicating mainly excitation losses by IRF emission. For weak excitation with 〈n〉 ≈ 1.4, almost an constant red shift versus time is observed. This result, and the previous finding that at weak excitation a nonthermal energy distribution in the ensemble of molecules exists, leads to the conclusion that intermolecular redistribution of vibrational energy in SF₆ is slow, and does not exceed the observed fluorescence duration (～1 ms).     

Optically pumped 15.90 μm SF6 laser

Optically pumped vibrational transition lasing has been achieved for the first time in a nonlinear molecule. Laser radiation at 628.74 ± 0.02 cm^?1 was generated from SF₆ using CO₂ TEA laser excitation. The SF₆ pumping is shown to be via absorption of two photons.     

Optoacoustic investigation of the mechanisms in the infrared optogalvanic effect

Simultaneous observations of the optogalvanic and optoacoustic effects were performed in CO₂, NH₃ and SF₆ discharges under irradiation by resonant infrared 10 μm laser radiation. The dependence of the galvanic and acoustic signals on the discharge current, and their time evolution following a switch of the laser radiation were investigated. The observations proved that the infrared optogalvanic effect occurs through two different mechanisms, a gas kinetic temperature dependence of the discharge parameters and a modification of the pion production through the vibrational molecular excitation.     

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.