A phase method of measuring the vibrational relaxation time for CO2 molecules

Conclusions The phase method can be applied to other compounds, but the choice of molecules and vibrational levels is restricted by the need for the level to have two allowed IR transitions. Also, the use of the method is restricted by the availability of strong IR sources.The phase method is analogous in concept to the spectrophone method [I] The advantage of the phase method is that it allows measurement of the lifetime for a single level no matter where it lies in the system of vibrational levels. Cascade transitions in deactivation (stepwise transformation of vibration energy to heat) greatly complicates the interpretation in the speetrophone method and essentially restricts its use to the first excited levels. Establishment of the phase zero is the main source of error in the spectrophone method and requires special calibration [5]. This problem has a simple solution in the phase method.In some cases the vibrational relaxation time can be determined from the amplitude dependence as affected by pressure, but this requires correction for the pressure dependence of the absorption coefficient for the exciting transition as well as that of the conditions for escape of the spontaneous emission through-out the vibration-rotation band.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 10, No. 2, pp. 252–255, February, 1969.     

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.     

Study of vibrational relaxation of CO2 molecules at the surface of a BaF2 crystal by the phase method

The phase method is used to experimentally study vibrational relaxation of CO₂ molecules found at the vibrational energy level 00°1 when they collide with the surface of a BaF₂ crystal. The probability of heterogeneous deactivation is determined for the temperature T=300°K in a calculation for one collision with an active center of the crystal of the surface _s=0.46±0.04 and with a surface layer of adsorbed molecules _g=0.06±0.01. The pressure of the gas in the working cell was varied in the range from 1 to 15 torr.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 49–53, July, 1986.     

Thermal rotations and relaxation of vibrational energy of excited dye molecules in solution

Measurements of polarization and decay time of fluorescence of dyes in solution as a function of excitation wavelength were performed. The rate of thermal rotational depolarization was found to be independent of vibrational energy excess. To explain the observed influence of excitation wavelength on the emission anisotropy, a change in the magnitude of torsional vibrations, in addition to possible mixing of states, is proposed.     

Calculation of vibrational energy transition rates in acoustic relaxation processes for excitable gas molecules

To research the correlation between vibrational energy transition rates and acoustic relaxation processes in excitable gases, the vibrational relaxation theory provided by Tanczos [J.Chem. Phys. 25, 439(1956)] is applied to calculate the energy transition rates of VibrationalVibrational(V-V) and Vibrational-Translational(V-T) energy transfer in gas mixtures. The results of calculation for the multi-relaxation processes in various gas mixtures, consisting of carbon dioxide, methane, chlorine, nitrogen, and oxygen at room temperature, demonstrate that the acoustic energy stagnated in every vibrational mode is coupled with each other through V-V energy exchanges. The vibrational excitation energy will relax through the V-T de-excitation path of the lowest mode because of its fastest V-T transition rate, resulting in that only one absorption peak can be measured for most of excitable gas mixtures. Thus, an effective model is provided to analyze how the vibrational energy transition rates affect the characteristics of acoustic relaxation processes and acoustic propagation in excitable gas mixtures.     

可激发气体分子声弛豫过程振动模式能量转移速率计算

研究可激发气体中振动模式能量转移速率和声弛豫过程形成的关系,将单一气体Tanczos弛豫方程理论[J.Chem.Phys.25,439(1956)]扩展应用于混合气体中振动模式的振动-振动(V-V)和振动-平动(V-T)能量转移速率的计算。在室温下CO₂,CH₄,CL₂,N₂和O₂组成的多种混合气体中,振动模式能量转移速率的计算结果表明:对于多个振动模式所形成的声复合弛豫过程,各振动模式的声激发能可由V-V能量转移相互耦合后传递给具有最快V-T转移速率的最低振动频率振动模式,再通过该振动模式的V-T转移退激发形成主弛豫过程。这种选择最快转移路径的声激发量弛豫方式,造成了大多数可激发气体中声弛豫吸收谱的实测数据只存在一个吸收峰的现象。从而提供了一个可通过计算微观振动能量转移速率分析混合气体声弛豫过程形成机理的理论模型。     

Investigation of vibrational relaxation of excimers

The excimer vibtational relaxation have been studied in the diffusional approximation, and stationary substantially non-equilibrium populations of high vibrational levels have been found. New formulae have been derived for quantum yield of UV lasing. Taking into account the vibrational relaxation the new effect of far-IR radiation amplification in the active media of excimer lasers is predicted.     

Rotational relaxation studies in CO2 molecules by means of a multiline tea CO2 laser system

If a CO₂ laser amplifier is injected by a single-frequency oscillator, the efficiency is limited. A multiline pulsed oscillator has been developed to overcome this limitation.     

Determination of the vibrational level populations and gas temperature by the gain of a CO2 gasdynamic laser in coupled mode transitions

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 52, No. 6, pp. 949–954, June, 1990.     

Analysis of a low-power CO2 laser performance as a function of gas flow rate

The performance of a flowing gas CO₂ laser is analysed and compared with a theoretical model which takes into account the gas flow rate and the CO₂ decomposition. Particular attention has been devoted to the characteristics of slow gas flow as a function of the gas mixture composition.     

Simultaneous measurements of absorption and vibrational relaxation time in CF2HCl molecules

Summary We describe in this paper a simple interferometric technique which allows a direct and simultaneous determination of energy absorption and of the vibrational-translational relaxation time of polyatomic molecules strongly excited by reasonant, infrared (10.6 μm) laser radiation. In particular, we have applied this method to the study of freon-22 (CF₂HCl), a medium-size molecule that, apart from its potential application in¹³C isotope separation, shows interesting absorption features in the 10 μm region. The results are also compared with our previous findings in SF₆. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Heterogeneous relaxation of molecule vibrational energy on metals

A mechanism of heterogeneous relaxation of a molecule vibrational energy on metal via conduction electrons is proposed. The probability of vibrational transition W of a molecule adsorbed on metal surface is calculated. The not very sharp dependence of W on the distance between the molecule and the metal surface, on metal parameters and on the molecular vibrational quantum provides a satisfactory explanation of the experimental data available.