C2 and CN formation by optical pumping of CO/Ar and Co/N2/Ar mixtures at room temperature

A continuous wave carbon monoxide laser is used to excite the vibrational mode of CO in CO/Ar and CO/N₂/Ar mixtures flowing through a gas absorption cell. High steady-state excitation of the CO vibrational mode (0.3 eV/molecule) is achieved, while a translational—rotational temperature near 300 K is maintained by the steady flow of cold gas into the cell. These non-equilibrium conditions result in extreme vibration—vibration pumping, population high-lying vibrational quantum levels (to V = 42) of CO. N₂ can also be pumped by vibrational energy transfer from CO. Under these conditions, C₂ and CN molecules are formed, and are observed to fluoresce on various electronic band transitions, notably C₂ Swan (A ³Π_g—X ³Π_u) and CN violet (B ²Σ⁺—X²Σ⁺).     

Spectroscopy and energy distribution study of the Cl + HI chemical laser

The spectral distribution of the pulsed, flash initiated Cl + HI → HCl(ν) + I chemical laser (3.6μ–4.0μ) was studied in both free running and grating selected systems. New transitions in both cavities are reported. The relative populations of the lasing HCl vibrational levels were measured using the grating selection technique. The relative distributions were found to be N₃/N₂ = 1.10 to 1.29 and N₂/N₁ = 2.23 to 2.32. A computational comparison between the chemical laser results and previous measurements by the infrared chemiluminescence method is made in view of vibrational V—R,T,V′ relaxation processes which may change the nascent population distribution.     

Characterization of supersonic beams of polyatomic molecules

Supersonic free jets and beams have been characterized in terms of the terminal Mach number, velocity spread, translational temperature and the average value of specific heat ratio (γ) pertinent to supersonic expansion. It has been found that for a polyatomic molecule, the average value of γ, used to describe the flow, depends upon the stagnation conditions. Vibrational relaxation of SF₆ as a representative of polyatomic molecules has been investigated using the “sudden freeze” model of Knuth and the relaxation rate equation model of Quah. Though the “sudden freeze” model predicts the experimental terminal vibrational temperature of Luijks et al., it overestimates cooling close to the nozzle exit. Quah's model shows that the vibrational relaxation cross section (σ_v) increases with decrease in temperature, contrary to the prediction of the Landau—Teller relaxation mechanism. This has been attributed to enhanced efficiency of vibrational relaxation at lower temperature due to facile exchange of internal energy with translational energy through the formation of quasi-resonant and van der Waals complexes.     

Laser induced energy-transfer studies in polyatomic mixtures: CH3F−CH3Cl

The rate of vibration energy transfer from CH₃F excited to the v₃ = 1 C—F stretching vibration to CH₃Cl has been measured by monitoring the rate of rise time of the CH₃Cl v₃ C-Cl stretch at 732 cm^?1 subsequent to laser pumping of the CH₃F. The V–V crossover rate was determined to be 35 ± 5 msec^?1 torr^?1 in mixtures of CH₃F-CH₃Cl and 48 ± 9 msec^?1 torr^?1 in mixtures of CH₃F-CH₃Cl and 40 torr of argon. The measured rate is interpreted in terms of the near resonant process

and is well in line with several predited and measured near resonant V–V crossovers between unlike collision partners. The possibility of obtaining an optically pumped three level infrared laser in CH₃Cl at 13.7 μ (corresponding to the v₃, ground state transition) is also discussed.     

Vibrational energy transfer from C2H4 to CO2 studied at low temperatures in a jet by infrared double resonance

In a mixed CO₂-C₂H₄ jet the populations of rotational levels in the ground andv ₂ (667 cm^?1) vibrational state of CO₂ are probed by color center laser absorption. The rotational distributions are well described by a rotational temperature. On the timescale of the expansion thev ₂ state does only relax through resonant deexcitation by CO₂ clusters. A 10% fraction of C₂H₄ molecules is excited into thev ₇ (949 cm^?1) level by CW CO₂ laser absorption, subsequently releasing energy into the expansion due to relaxation to lower C₂H₄ vibrational states and to thev ₂ mode of CO₂. Observed are the induced rise of rotational temperature and the increase ofv ₂ level population. By probing at several distances from the nozzle the temperature range from 30–155 K is covered. The vibrational transfer of the excited C₂H₄ to thev ₂ level of CO₂ has a near quadratic inverse temperature dependence, increasing by a factor of 40 when the temperature is lowered from 155 K to 30 K.     

On the vibrational structure of methyl iodide. II. relaxation pathways in the 3000 cm−1 energy regime

Model calculations for state collision induced vibrational relaxation rates are performed. The model includes intramolecular couplings to fourth order. It is shown that Fermi resonance interactions between the v_i CH-stretching mode and overtones or higher order combination tones are essential to understand the rapid energy relaxation into these states.     

Vibrational energy transfer in CH3I

Previous works have reported vibration—vibration and vibration—translation transfer rates in the methyl halides. Using the technique of laser induced infrared fluorescence we have studied energy transfer in the concluding member of this series, CH₃I. Following excitation by resonant lines of a Q-switch CO₂ laser, infrared fluorescence has been observed from the v₂, v₅ as well as the 2v₅, v₁, v₄ vibrational energy levels of CH₃I. All the observed states exhibit a single exponential decay rate of 23 ± 2 ms^?1 torr^?1. Measurements have also been made on deactivation of the various modes by rare gases. The risetime of the v₂, v₅ levels was found to be approximately 101 ± 20 ms^?1 torr^?1, while that of the 2v₅, v₁, v₄ levels was approximately 225 ± 45 ms^?1 torr^?1. Fluorescence was not detected from the v₃ level. These results are discussed in terms of SSH type theoretical calculations, and comparison is made with the results obtained for other members of the methyl halide series, namely CH₃F, CH₃Cl and CH₃Br.     

V—V,V—R,T transfer in triatomic molecules. Results for ONF

The laser-induced fluorescence technique is applied to study vibrational energy transfer in pure ONF. Different vibrational modes are excited using a TEA CO₂ laser and the rise and fall of ν₁, ν₂, and (ν₁ + ν₃) fluorescence is detected. These measurements yield a detailed picture of V—V exchange in the region of the fundamentals and V—R,T transfer to rotational and translational degrees of freedom. The relaxation behavior of ONF is compared with that of ONCI and other triatomic molecules.     

Mode-to-mode vibrational energy flow in S1 benzene

Resolved fluorescence spectra from low pressures of benzene with nine added gases have been used to follow mode-to-mode vibrational relaxation in the S₁ state of benzene under “single-collision” conditions. Cw pumping of the S₁ fundamental 6¹ (ν″₆ = 522 cm^?1) allows study of collisional vibrational energy flow into each of four channels. Two channels consist of flow into single levels, and the others represent flow into unresolved pairs of levels. The mode-to-mode cross sections are much larger than those usually observed in ground electronic states, being near gas kinetic even for partners transferring energy by VT, R processes alone. The mode-to-mode transfer has highly specific patterns, with roughly seventy percent of the transfer going into the four channels in spite of many other nearby levels. The largest cross sections are always to a level 237 cm^?1 above the initial level rather than to a level nearly resonant (ΔE = 7 cm^?1) with the initia l level. A common pattern of flow occurs for the four gases transferring energy by VT, R processes alone, and another common pattern is established for the five gases which can also use VV transfers. With the exception of one channel, VV resonances with vibrationally complex partners increase cross sections by less than a factor of two over that provided by the VT, R path. VV transfers have a similarly small effect on the overall vibrational relaxation rate out of the initial level 6¹. Both the flow patterns and the VV versus VT, R competitions are accounted for with an extremely simple and general set of propensity rules taken directly from SSH calculations made by others for vibrational relaxation in ground electronic states. The rules are based on the degeneracies of the final levels, the number of vibrational quantum changes, and the amount of energy exchanged between vibrational and translational/rotational degrees of freedom. The rules seem general to relaxation in both ground and excited electronic states, whereas large cross sections seem a special property of the excited state. The cross sections for collision partners SF₆ and perfluorohexane are small relative to those for other partners with similar vibrational complexity and mass.     

Dependence of the probability of VT-VV coupled transitions on vibrational quantum numbers

The dependence of the probability of v - 1 → v vibrational excitations in molecule-molecule collisions on the vibrational quantum number v has been studied for v up to 7. This nominally VT energy transfer process can be strongly affected by the participation of VV mode particularly among high-lying states. The dependences of the probabilities on v among such states are shown to be non-linear largely due to the VT-VV intermode coupling. A sample calculation of the dependence in iodine molecules shows that the coupling is very strong when the temperature is high and that the probabilities seriously deviate from the linear relation P_v - 1.0 → v.0 = vP_{0.0 → 1.0}, where molecule 1 undergoes transition from v - 1 to v, while molecule 2 remains in the ground state.     

Vibrational relaxation of ethylene oxide and ethylene oxide-rare-gas mixtures

The collision-induced vibrational energy relaxation of ethylene oxide (C₂H₄O) was studied by means of laser-induced fluorescence. The time-dependent population of the vibrational modes v₃ and v₅/v₁₂ was measured after excitation of CH-stretching vibrations near 3000 cm^?1. Rate constants for the vibrational energy transfer by collisions with C₂H₄O and the rare gases are deduced, and a simplified model for the vibrational relaxation of C₂H₄O is discussed.     

A laser induced fluorescence study of vibrational energy transfer processes in cyclopropane

Results of infrared laser induced fluorescence studies on cyclopropane are presented. Molecules were excited from the ground state to the v₁₀ level of cyclopropane using a Q-switched CO₂ laser operating on either the P(14) or P(20) transition of the 9.6 μ branch. Fluorescence was observed from the v₆, v₈, v₁₀ + v₁₁ and v₅ + v₁₀ levels of cyclopropane. The self-deactivation of vibrationally excited cyclopropane through V → T/R processes was found to have a rate of 8.0 ± 1.5 ms^?1 torr^?1. Deactivation by rare gas collisions was also studied with comparison to simple V → T and V → R theories. V → V equilibration processes are discussed involving the v₆, v₈, v₁₀, v₁₁, and v₁₀ + v₁₁ levels.     

Vibrational relaxation in COF2 and Xe,C2H6 mixtures following intense laser excitation

The VR,T rate in COF₂ was measured directly by the ultrasonic absorption technique. The laser-induced fluorescence method was used to study VV exchange between the strongly pumped ν₂, ν₁ manifold and other vibrational degrees of freedom. At a few Torr a transition of the μm fluorescence from a single exponential decay to a relaxation spectrum is observed. This relaxation spectrum was analyzed by determining the “differential decay rate” for successive small time intervals. The relaxation spectrum is not changed by a pressure increase from ≈ 4 to 15 Torr. Similarly, relatively large amounts of Xe must be added before a change in the relaxation behavior of COF₂ can be detected. C₂H₆ is a very effective quencher of the 5μm fluorescence.     

Measurement of excited state population decay time in NH3 by optical adiabatic rapid passage

A strong Q-switched N₂O laser capable of 60 MHz frequency sweep is used to induce population inversion by optical adiabatic rapid passage on the ν₂[asQ(8,7)] transition of ¹⁴NH₃. The fast inversion and the subsequent return to equilibrium are detected by a cw weak counterpropagating N₂O laser, and are used to measure the pressure dependence of excited state population relaxation time T₁ for the infrared transition of interest. this decay is found to be 3.6 times slower than the correpsonding decay in the ground state, an effect which may be explained by the larger inversion energy separation in the excited state of NH₃.     

Fermi-coupled spherically adapted effective states in the collisionless multiphoton excitation of SF6

A calculation method for the collisionless multiphoton excitation of SF₆ by intense CO₂ laser light up to a chain of parallel nv₃, (n - 1)v₃ + v₂ + v₆ … vibrational-rotational ladders linked by Fermi interaction is described. Spherically adapted effective states suitable to the purpose are defined, and matrix elements for multiphoton excitation in the rotatingwave approximation effective hamiltonian formalism are given in this basis. The method is aimed at the investigation of population transfer between the cited parallel vibrational ladders, and is suitable for computer-calculation programmation.     

Relaxation of the individual vibrational levels of carbon monoxide following shock heating at 2100 K

The increases in the populations of the vibrational levels v = 1 to v = 5 in CO which is undergoing thermal vibrational relaxation at 2100 K have been monitored using a cw CO laser. The experiments have been carried out in a very narrow temperature range for mixtures of CO, Ar and He. Under these conditions the first part of the relaxation region is clearly visible, and it has been possible to compare the population growths of different vibrational levels under the same conditions. We have shown that the curve for the increase in the population of the level v = 1 with time is clearly different from those of the higher levels. It has been shown that all of the vibrational levels studied in this work on CO relax with a common vibrational temperature, as postulated in the model of Shuler and co-workers. The results reported here are qualitatively different from those presented by Chow and Greene on HI.     

Mode-to-mode vibrational energy transfer in D2CO: Evidence of coriolis-enhanced rotational selectivity

Infrared—ultraviolet double resonance spectroscopy is used to demonstrate rapid collision-induced V-V transfer between the v₆ and v₄ vibrational manifolds of D₂CO. The rate of transfer is at least gas-kinetic and is explained in terms of Coriolis coupling and rotationally specific, quasi-resonant relaxation channels     

Microviscosity dependence of the Raman band shape of methyl-isobutyl ketone

The Raman band shape analysis of the CO stretching mode of vibration of methyl-isobutyl ketone in solution phase reveals that macroscopic consideration of hydrodynamic force is not sufficient to correlate the vibrational relaxation rate (τ_v⁻¹) with parameter ƒ(ϱ, η, n), involving dynamic viscosity (η). The band shape analysis was therefore attempted taking the microscopic parameter, microviscosity (η_m) into account through a modified parameter ƒ_m. The correlation of τ_v⁻¹ with ƒ_m is reported.     

Laser raman spectra of the stable low-temperature phase of ferrocene

Laser Raman spectra of ferrocene crystal are recorded for the stable (orthorhombic) and metastable (triclinic) low-temperature phases, and the stable and undercooled (monoclinic) high-temperature phases.The skeletal vibrational modes [v₄(A_1g) and v₁₆(E_1g)], the CH bending (⊥e) mode [v₂₅(E_2g)], and the lattice modes below 100 cm^?1 show characteristic changes among these phases.