Equilibration of vibrationally excited OH in atomic and diatomic bath gases

In this work, a computational model of state-to-state energy flow in gas ensembles is used to investigate collisional relaxation of excited OH, present as a minor species in various bath gases. Rovibrational quantum state populations are computed for each component species in ensembles consisting of 8000 molecules undergoing cycles of binary collisions. Results are presented as quantum state populations and as (approximate) modal temperatures for each species after each collision cycle. Equilibration of OH is slow with Ar as the partner but much faster when N(2) and/or O(2) forms the bath gas. This accelerated thermalization is shown to be the result of near-resonant vibration-vibration transfer, with vibrational de-excitation in OH matched in energy by excitation in bath molecules. Successive near-resonant events result in an energy cascade. Such processes are highly dependent on molecule pair and on initial OH vibrational state. OH rotational temperatures initially increase, but at equilibration, they are lower than those of other modes. Possible reasons for this observation in molecules such as OH are suggested. There are indications of an order of precedent in the equilibration process, with vibrations taking priority over rotations, and potential explanations for this phenomenon are discussed.     

Competitive partitioning of rotational energy in gas ensemble equilibration

A wide-ranging computational study of equilibration in binary mixtures of diatomic gases reveals the existence of competition between the constituent species for the orbital angular momentum and energy available on collision with the bath gas. The ensembles consist of a bath gas AB(v;j), and a highly excited minor component CD(v';j'), present in the ratio AB:CD = 10:1. Each ensemble contains 8000 molecules. Rotational temperatures (T(r)) are found to differ widely at equilibration with T(r)(AB)/T(r)(CD) varying from 2.74 to 0.92, indicating unequal partitioning of rotational energy and angular momentum between the two species. Unusually, low values of T(r) are found generally to be associated with diatomics of low reduced mass. To test effects of the equi-partition theorem on low T(r) we undertook calculations on HF(6;4) in N(2)(0;10) over the range 100-2000 K. No significant change in T(r)(N2)/T(r)(HF) was found. Two potential sources of rotational inequality are examined in detail. The first is possible asymmetry of -Δj and +Δj probabilities for molecules in mid- to high j states resulting from the quadratic dependence of rotational energy on j. The second is the efficiency of conversion of orbital angular momentum, generated on collision with bath gas molecules, into molecular rotation. Comparison of these two possible effects with computed T(r)(AB)/T(r)(CD) shows the efficiency factor to be an excellent predictor of partitioning between the two species. Our finding that T(r) values for molecules such as HF and OH are considerably lower than other modal temperatures suggests that the determination of gas ensemble temperatures from Boltzmann fits to rotational distributions of diatomics of low reduced mass may require a degree of caution.     

Effects of argon dilution on the translational and rotational temperatures of SiH in silane and disilane plasmas

The effects of argon dilution on the translational and rotational temperatures of SiH in both silane and disilane plasmas have been investigated using the imaging of radicals interacting with surfaces (IRIS) technique. The average rotational temperature of SiH determined from the SiH excitation spectra is approximately 500 K in both SiH(4)/Ar and Si(2)H(6)/Ar plasmas, with no obvious dependence on the fraction of argon dilution. Modeling of kinetic data yields average SiH translational temperatures of approximately 1000 K, with no dependence on the fraction of argon in the SiH(4)/Ar plasmas within the studied range. In the Si(2)H(6)/Ar plasmas, however, the translational temperature decreases from approximately 1000 to approximately 550 K as the Ar fraction in the plasma increases. Thus, at the highest Ar fractions, the translational and rotational temperatures are nearly identical, indicating that the SiH radicals are thermally equilibrated. The underlying chemistry and mechanisms of SiH energy equilibration in Ar-diluted plasmas are discussed.     

Detection of OH radical in laser induced photodissociation of tetrahydrofuran at 193 nm

On excitation at 193 nm, tetrahydrofuran (THF) generates OH as one of the photodissociation products. The nascent energy state distribution of the OH radical was measured employing laser induced fluorescence technique. It is observed that the OH radical is formed mostly in the ground vibrational level, with low rotational excitation (approximately 3%). The rotational distribution of OH (v"=0,J) is characterized by rotational temperature of 1250+/-140 K. Two spin-orbit states, 2Pi3/2 and 2Pi1/2 of OH are populated statistically. But, there is a preferential population in Lambda doublet levels. For all rotational numbers, the 2Pi+(A') levels are preferred to the 2Pi-(A") levels. The relative translational energy associated with the photoproducts in the OH channel is calculated to be 17.4+/-2.2 kcal mol-1, giving an fT value of approximately 36%, and the remaining 61% of the available energy is distributed in the internal modes of the other photofragment, i.e., C4H7. The observed distribution of the available energy agrees well with a hybrid model of energy partitioning, predicting an exit barrier of approximately 16 kcal mol-1. Based on both ab initio molecular orbital calculations and experimental results, a plausible mechanism for OH formation is proposed. The mechanism involves three steps, the C-O bond cleavage of the ring, H atom migration to the O atom, and the C-OH bond scission, in sequence, to generate OH from the ground electronic state of THF. Besides this high energy reaction channel, other photodissociation channels of THF have been identified by detecting the stable products, using Fourier transform infrared and gas chromatography.     

Dynamics of OH radical generation in laser-induced photodissociation of tetrahydropyran at 193 nm

Tetrahydropyran (THP) undergoes photodissociation on excitation with ArF laser at 193 nm, generating OH radical as one of the transient photoproducts. Laser-induced fluorescence technique is used to detect the nascent OH radical and measure its energy state distribution. The OH radical is formed mostly in the ground vibrational level (v"=0), with low rotational excitation. The rotational distribution of OH (v"=0,J) is characterized by a temperature of 433+/-31 K, corresponding to a rotational energy of 0.86+/-0.06 kcalmol. Two Lambda-doublet levels, 2Pi+(A') and 2Pi-(A"), and the two spin-orbit states, the 2Pi(3/2) and 2Pi(1/2), of OH are populated statistically for all rotational levels. The relative translational energy associated with the photoproducts in the OH channel is calculated to be 21.9+/-3.2 kcal mol(-1), from the Doppler-broadened linewidth, giving an ft value of approximately 43%, and most of the remaining 57% of the available energy is distributed in the internal modes of the other photofragment, C5H9. The observed distribution of the available energy is explained well, using a hybrid model of energy partitioning, with an exit barrier of 40 kcal mol(-1). The potential-energy surface of the reaction channel was mapped by ab initio molecular-orbital calculations. Based on experimental and theoretical results, a mechanism for OH formation is proposed. Electronically excited THP relaxes to the ground electronic state, and from there, a sequence of reactions takes place, generating OH. The proposed mechanism first involves C-O bond scission, followed by a 1,3 H atom migration to O atom, and finally, the C-OH bond cleavage giving OH.     

Near-resonant energy transfer from highly vibrationally excited OH to N2

The probability per collision P(T) of near-resonant vibration-to-vibration energy transfer (ET) of one quantum of vibrational energy from vibrational levels nu=8 and nu=9 of OH to N(2)(nu=0), OH(nu)+N(2)(0)-->OH(nu-1)+N(2)(1), is calculated in the 100-350 K temperature range. These processes represent important steps in a model that explains the enhanced 4.3 microm emission from CO(2) in the nocturnal mesosphere. The calculated energy transfer is mediated by weak long-range dipole-quadrupole interaction. The results of this calculation are very sensitive to the strength of the two transition moments. Because of the long range of the intermolecular potential, the resonance function, a measure of energy that can be efficiently exchanged between translation and vibration-rotation degrees of freedom, is rather narrow. A narrow resonance function coupled with the large rotational constant of OH is shown to render the results of the calculation very sensitive to the rotational distribution, or the rotational temperature if one exists, of this molecule. The calculations are carried out in the first and second orders of perturbation theory with the latter shown to give ET probabilities that are an order of magnitude larger than the former. The reasons for the difference in magnitude and temperature dependence of the first- and second-order calculations are discussed. The results of the calculations are compared with room temperature measurements as well as with an earlier calculation. Our calculated results are in good agreement with the room temperature measurements for the transfer of vibrational energy for the exothermic OH(nu=9) ET process but are about an order lower than the room temperature measurements for the exothermic OH(nu=8) ET process. The cause of this discrepancy is explored. This calculation does not give the large values of the rate coefficients needed by the model that explains the enhanced 4.3 microm emission from CO(2) in the nocturnal mesosphere.     

Quantum state-resolved energy redistribution in gas ensembles containing highly excited N2

A computational model is used to quantify the evolution of quantum state populations as highly vibrationally excited (14)N(2) ((14)N(2)?) equilibrates in various bath gases. Multicollision energy disposal follows general principles established in related single collision processes. Thus when state-to-state routes permit, maximum amounts of energy are deposited into partner species by direct vibration-to-vibration (V-V) exchange. When these pathways are absent, e.g., when Ar is the bath species, relaxation is very slow and multistaged. Conversely, in a bath of v = 0 (14)N(2) molecules, 16 vibrational quanta (Δv = ± 8) are resonantly exchanged from (v;j) = (8;10) with vibrational equilibration so rapid that rotation and translation still lag far behind after 1000 collisions. Near-resonant V-V exchange dominates the initial phase when (15)N(2) forms the bath gas and although some rotational warming occurs, vibrational modes remain decoupled from, and significantly hotter than, the low heat capacity modes. These forms of behavior seem likely to characterize excited and bath species that have closely similar vibration and rotation constants. More generic in nature is (14)N(2) in O(2) or in a mixture that closely resembles air. Here, asymmetric V-V exchange is a dominant early feature in ensemble evolution but energy differences in the key vibration and rotation quanta lead to V-V energy defects that are compensated for by the low energy modes. This results in much more rapid ensemble equilibration, generally within 400-500 collisions, when O(2) is present even as a minor constituent. Our results are in good general agreement with those obtained from experimental studies of N(2) plasmas both in terms of modal temperatures and initial (first collision cycle) cross-sections.     

Host-assisted intramolecular vibrational relaxation at low temperatures: OH in an argon cage

The vibrational relaxation of hydroxyl radicals in the A (2)Sigma(+) (v=1) state has been studied using the semiclassical perturbation treatment at cryogenic temperatures. The radical is considered to be trapped in a closest packed cage composed of the 12 nearest argon atoms and undergoes local translation and hindered rotation around the cage center. The primary relaxation pathway is towards local translation, followed by energy transfer to rotation through hindered-to-free rotational transitions. Free-to-free rotational transitions are found to be unimportant. All pathways are accompanied by the propagation of energy to argon phonon modes. The deexcitation probability of OH(v=1) is 1.3 x 10(-7) and the rate constant is 4.7 x 10(5) s(-1) between 4 and 10 K. The negligible temperature dependence is attributed to the presence of intermolecular attraction (>kT) in the guest-host encounter, which counteracts the T(2) dependence resulting from local translation. Calculated relaxation time scales are much shorter than those of homonuclear molecules, suggesting the importance of the hindered and free motions of OH and strong guest-host interactions.     

Dissociative excitation of water by metastable argon

The reaction Ar(²P_2,0) + H₂O → Ar + H + OH(A²Σ⁺)was studied in crossed molecular beams by observing the luminescence from OH(A²Σ⁺). No significant dependence of the spectrum on collision energy was found over the 22–52 meV region. Spectral simulation was used to obtain the OH(A) vibrational distribution and rotational temperature, assuming a Boltzmann rotational distribution. Since predissociation is known to strongly affect the rovibrational distribution, the individual rotational state lifetimes were included in the simulation program and were used to obtain the average vibrational state lifetimes. Excellent agreement with experiment was obtained for vibrational population ratios N₀/N₁/N₂ of 1.00/ 0.40/0.013 and a rotational temperature of 4000 K. Correction for the different average vibrational lifetimes gave formation rate ratios P₀/P₁/P₂ of 1.00/0.49/0.25. The differences between these results and those from flowing afterglow studies on the same system are discussed. Three reaction mechanisms are considered, and the vibrational prior distributions are calculated from a simple density-of-states model. Only fair agreement with experiment is obtained. The best agreement for the mechanisms giving OH(A) in two 2-body dissociation steps is obtained by assuming 1.0 eV of internal energy remains in the second step. The OH(A) vibrational population distribution of the present work is similar to that found in the photolysis of H₂O at 122 nm, where there is 1.10 eV of excess internal energy.     

Role of powering geometries and sheath gas composition on operation characteristics and the optical emission in the liquid sampling-atmospheric pressure glow discharge

Characterization of the liquid sampling-atmospheric pressure glow discharge optical emission spectroscopy (LS-APGD-OES) source is described with regards to applications in low-flow separations such as capillary liquid chromatography and electrophoresis. Four powering modes are investigated, including the effects of the individual modes on current–voltage characteristics, analyte emission response, and temporal broadening of flow injection profiles. A concentric sheath gas is employed to stabilize the solution delivery at low liquid flow rates. Sheath gas composition (N₂ or He) effects analyte emission responses as well as gas phase rotational and excitation temperatures. The respective powering modes both measures of temperature, with the OH rotational gas temperatures ranging from ∼2100 to 3000 K and the Fe (I) excitation temperatures ranging from ∼2400 to 3600 K. Rotational temperature values increase slightly when helium is employed as a sheath gas as opposed to nitrogen, with the corresponding excitation temperatures increasing somewhat as well. Analytical response curves for Na and Hg in the various powering modes demonstrate good linearity, with the limits of detection for the analytes found to be on the order of ∼4–10 ppm for 5 μl injections; equating to absolute detection limits of between 20 and 45 ng. It is believed that the approach demonstrated here suggests further improvements that will permit applications in a wide variety of aqueous solution analyses where low-flow rates and limited volumes are encountered.     

Dynamics of N-OH bond dissociation in cyclopentanone and cyclohexanone oxime at 193 nm: laser-induced fluorescence detection of nascent OH (v', J')

Cyclohexanone oxime (CHO) and cyclopentanone oxime (CPO) in the vapor phase undergo N-OH bond scission upon excitation at 193 nm to produce OH, which was detected state selectively employing laser-induced fluorescence. The measured energy distribution between fragments for both oximes suggests that in CHO the OH produced is mostly vibrationally cold, with moderate rotational excitation, whereas in CPO the OH fragment is also formed in v' = 1 (~2%). The rotational population of OH (v' = 0, J') from CHO is characterized by a rotational temperature of 1440 ± 80 K, whereas the rotational populations of OH (v' = 0, J') and OH (v' = 1, J') from CPO are characterized by temperatures of 1360 ± 90 K and 930 ± 170 K, respectively. A high fraction of the available energy is partitioned to the relative translation of the fragments with f(T) values of 0.25 and 0.22 for CHO and CPO, respectively. In the case of CHO, the Λ-doublet states of the nascent OH radical are populated almost equally in lower rotational quantum levels N', with a preference for Π(+) (A') states for higher N'. However, there is no preference for either of the two spin orbit states Π(3/2) and Π(1/2) of OH. The nascent OH product in CPO is equally distributed in both Λ-doublet states of Π(+) (A') and Π(-) (A') for all N', but has a preference for the Π(3/2) spin orbit state. Experimental work in combination with theoretical calculations suggests that both CHO and CPO molecules at 193 nm are excited to the S(2) state, which undergoes nonradiative relaxation to the T(2) state. Subsequently, molecules undergo the N-OH bond dissociation from the T(2) state with an exit barrier to produce OH (v', J').     

Potential surfaces and dynamics of the O(3P)+H2O(X1A1)-->OH(X2pi)+OH(X2pi) reaction

We present global potential energy surfaces for the three lowest triplet states in O(3P)+H2O(X1A1) collisions and present results of classical dynamics calculations on the O(3P)+H2O(X1A1)-->OH(X2pi)+OH(X2pi) reaction using these surfaces. The surfaces are spline-based fits of approximately 20,000 fixed geometry ab initio calculations at the complete-active-space self-consistent field+second-order perturbation theory (CASSCF+MP2) level with a O(4s3p2d1f)/H(3s2p) one electron basis set. Computed rate constants compare well to measurements in the 1000-2500 K range using these surfaces. We also compute the total, rovibrationally resolved, and differential angular cross sections at fixed collision velocities from near threshold at approximately 4 km s(-1) (16.9 kcal mol(-1) collision energy) to 11 km s(-1) (122.5 kcal mol(-1) collision energy), and we compare these computed cross sections to available space-based and laboratory data. A major finding of the present work is that above approximately 40 kcal mol(-1) collision energy rovibrationally excited OH(X2pi) products are a significant and perhaps dominant contributor to the observed 1-5 micro spectral emission from O(3P)+H2O(X1A1) collisions. Another important result is that OH(X2pi) products are formed in two distinct rovibrational distributions. The "active" OH products are formed with the reagent O atom, and their rovibrational distributions are extremely hot. The remaining "spectator" OH is relatively rovibrationally cold. For the active OH, rotational energy is dominant at all collision velocities, but the opposite holds for the spectator OH. Summed over both OH products, below approximately 50 kcal mol(-1) collision energy, vibration dominates the OH internal energy, and above approximately 50 kcal mol(-1) rotation is greater than vibrational energy. As the collision energy increases, energy is diverted from vibration to mostly translational energy. We note that the present fitted surfaces can also be used to investigate direct collisional excitation of H2O(X1A1) by O(3P) and also OH(X2pi)+OH(X2pi) collisions.     

Direct Vibrational Energy Transfer in Monomeric Water Probed with Ultrafast Two Dimensional Infrared Spectroscopy

Vibrational relaxation dynamics of monomeric water molecule dissolved in d-chloroform solution were revisited using the two dimensional Infrared (2D IR) spectroscopy. The vibrational lifetime of OH bending in monomeric water shows a bi-exponential decay. The fast component (T₁=(1.2±0.1) ps) is caused by the rapid population equilibration between the vibrational modes of the monomeric water molecule. The slow component (T₂=(26.4±0.2) ps) is mainly caused by the vibrational population decay of OH bending mode. The reorientation of the OH bending in monomeric water is determined with a time constant of τ=(1.2±0.1) ps which is much faster than the rotational dynamics of water molecules in the bulk solution. Furthermore, we are able to reveal the direct vibrational energy transfer from OH stretching to OH bending in monomeric water dissolved in d-chloroform for the first time. The vibrational coupling and relative orientation of transition dipole moment between OH bending and stretching that effect their intra-molecular vibrational energy transfer rates are discussed in detail.     

Activation energy and nonequilibrium effects in thermal reactions

Calculations of the nonequilibrium rate constant for the model system H₂O₂ + M → 2 OH + M over the temperature range of 300–1900°K, assuming that only vibrational, or that both vibrational and rotational, energy is transferred in a collision, show that (1) inefficient energy transfer leads to a distinctly non-Arrhenius temperature dependence, the nonlinearity being in principle different for different M, and (2) despite different activation energies for different M, the order of M efficiencies is preserved throughout the temperature range. A reversal of M efficiencies can occur only if there is a change of mechanism of the reaction over the temperature range investigated.     

The water hexamer: cage, prism, or both. Full dimensional quantum simulations say both

State-of-the-art quantum simulations on a full-dimensional ab initio potential energy surface are used to characterize the properties of the water hexamer. The relative populations of the different isomers are determined over a wide range of temperatures. While the prism isomer is identified as the global minimum-energy structure, the quantum simulations, which explicitly include zero-point energy and quantum thermal motion, predict that both the cage and prism isomers are present at low temperature down to almost 0 K. This is largely consistent with the available experimental data and, in particular, with very recent measurements of broadband rotational spectra of the water hexamer recorded in supersonic expansions.     

大气压射频等离子体化学气相沉积TiO2体系的发射光谱诊断

开展了大气压射频(RF)等离子体化学气相沉积(PCVD)TiO₂放电体系的发射光谱诊断研究, 分别考察了氧气分压、钛酸四异丙酯(TTIP)分压和输入功率对氧原子谱线相对强度、氩原子激发温度、OH振动温度以及转动温度的影响. 结果表明: 随着氧气分压的增加, 氧原子谱线相对强度先迅速增加至峰值后缓慢下降, OH振动温度缓慢增加, 而氩原子激发温度和OH转动温度基本不变. 随着TTIP 分压的增加, 氧原子谱线相对强度下降, 氩原子激发温度没有明显变化, 而OH振动温度和转动温度增加. 随着输入功率的增加, 氧原子谱线相对强度下降, 氩原子激发温度、OH振动温度和转动温度升高.     

Identification of Hydroxyl on Ni(111)

Hydroxyl (OH) is identified and characterized on the Ni(111) surface by high‐resolution electron energy loss spectroscopy. We find clear evidence of stretching, bending, and translational modes that differ significantly from modes observed for H₂O and O on Ni(111). Hydroxyl may be produced from water by two different methods. Annealing of water co‐adsorbed with atomic oxygen at 85 K to above 170 K leads to the formation of OH with simultaneous desorption of excess water. Pure water layers treated in the same fashion show no dissociation. However, the exposure of pure water to 20 eV electrons at temperatures below 120 K produces OH in the presence of adsorbed H₂O. In combination with temperature‐programmed desorption studies, we show that the OH groups recombine between 180 and 240 K to form O and immediately desorbing H₂O. The lack of influence of co‐adsorbed H₂O at 85 K on the O? H stretching mode indicates that OH does not participate in a hydrogen‐bonding network.     

Fluorescence excitation and excited state intramolecular proton transfer of jet-cooled naphthol derivatives: Part 1. 1-Hydroxy-2-naphthaldehyde

The S(0) → S(1) fluorescence excitation spectrum of jet-cooled 1H2N with origin at 25484 cm(-1) has been measured. Twelve totally symmetric modes and five non-totally symmetric modes have been assigned in the excitation spectrum. Theoretical calculations at DFT B3LYP/6-31G** and CIS/6-31G** levels indicate that the 1H2N molecular geometry is more planar in the S(1) state than in the ground state. The geometry of the naphthalene ring changes upon excitation and promotes a number of totally symmetric ring stretching modes, in the excitation spectrum. As a result of the geometry change upon excitation a number of non-totally symmetric modes gain intensity. Based on a rotational envelope fitting procedure the average excited rotational state lifetime was estimated to be between 7 and 16 ps for 0 ≤E≤ hc × 800 cm(-1) (E is excess energy above the S(1) origin). The decay rate coefficients, k, of the rotational S(1) states, are not constant over this range of excess energies. By applying a Golden Rule model, it was determined that internal conversion to S(0) is unlikely to be the sole non-radiative process contributing to the decay of the excited states. It was concluded that excited state intramolecular proton transfer (ESIPT) plays a role in the observed behaviour of the rate co-efficient with excess energy. The observation of (i) a sharp increase in rate coefficient, k, above an excess energy of ～550 cm(-1), and (ii) a significant number of high intensity fluorescence excitation spectrum features above an excess energy of ～700 cm(-1), may indicate the presence of an energy barrier of ～550 cm(-1), between the enol and keto geometries in the S(1) state. This result supports the conclusions of S. De, S. Ash, S. Dalai and A. Misra, J. Mol. Struc. Theochem, 2007, 807, 33-41, who estimated a barrier to ESIPT of ～750 cm(-1). It was concluded that ESIPT occurs in 1H2N, across an energy barrier with a rate constant, k(pt)≤ 10(11) s(-1). Hence, at low excess energies (≤ 550 cm(-1)), the observed emission band originates predominantly from the keto tautomer. Above an excess energy of ～1600 cm(-1), 1H2N decays predominantly via a non-radiative mechanism.     

Energy transfer between polyatomic molecules II: Energy transfer quantities and probability density functions in benzene, toluene, p-xylene, and azulene collisions

Collisional energy transfer, CET, is of major importance in chemical, photochemical, and photophysical processes in the gas phase. In Paper I of this series (J. Phys. Chem. B 2005, 109, 8310) we have reported on the mechanism and quantities of CET between an excited benzene and cold benzene and Ar bath. In the present work, we report on CET between excited toluene, p-xylene, and azulene with cold benzene and Ar and on CET of excited benzene with cold toluene, p-xylene, and azulene. We compare our results with those of Paper I and report average vibrational, rotational, and translational energy quantities, , transferred in a single collision. We discuss the effect of internal rotation on CET and the identity of the gateway modes in CET and the relative role of vibrational, rotational, and translational energies in the CET process, all that as a function of temperature and excitation energy. Energy transfer probability density functions, P(E,E'), for the various systems are reported and the shape of the curves for various systems and initial conditions is discussed. The major findings for polyatomic-polyatomic collisions are: CET takes place mainly via vibration-to-vibration energy transfer assisted by overall rotations. Internal free rotors in the excited molecule hinder energy exchange while in the bath molecule they do not. Energy transfer at low temperatures and high temperatures is more efficient than that at intermediate temperatures. Low-frequency modes are the gateway modes for energy transfer. Vibrational temperatures affect energy transfer. The CET probability density function, P(E,E'), is convex at low temperatures and can be concave at high temperatures. A mechanism that explains the high values of and the convex shape of P(E,E') is that in addition to short impulsive collisions there are chattering collisions where energy is transferred in a sequence of short encounters during the lifetime of the collision complex. This also leads to the observed supercollision tail at the down wing of P(E,E'). Polyatomic-Ar collisions show mechanistic similarities to polyatomic-polyatomic collisions, but there are also many dissimilarities: internal rotations do not inhibit energy transfer, P(E,E') is concave at all temperatures, and there is no contribution of chattering collisions.     

Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the nu = 1-5 vibrational states of the OH stretching transitions. Cross sections for nu = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the nu OH = 4 transition with thermal excitation of low frequency modes or rotational motion and nu OH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.