Absorption Cross-section Measurements Research Articles

Measurement of high-temperature absorption cross-sections using an optical cell with a non-uniform temperature distribution

A mathematical method to enable absorption cross-section measurements using an optical cell with a non-uniform temperature distribution is formulated, validated and experimentally demonstrated in this study. The motivation of the proposed method is to facilitate high-temperature spectroscopic studies in the long-wavelength mid-IR region, and to offer an alternative to highly engineered optical cells. The method is based on virtual segmentation of the non-uniform temperature field within an optical cell into bins, each having a sufficiently uniform temperature. By collecting a set of absorbance measurements corresponding to unique temperature profiles and expressing the temperature dependence of the absorption cross-section in terms of a model with limited number of unknowns, a closed-form system of equations is obtained which can be solved to evaluate absorption cross-sections. It is shown, through a set of simulated validation cases, that modeling the temperature dependence in terms of a third order polynomial results in accurate reconstruction of the cross-section spectra for a wide range of cases. Piece-wise polynomials and an alternative nonlinear model are proposed for improved accuracy and to model potentially complex temperature dependencies of the absorption cross-sections. To demonstrate the application of the proposed method, an optical cell with a non-uniform temperature profile was used to measure the cross-section spectra of methane over 1280 – 1330 cm-1 at temperatures up to 523 K. The proposed method is expected to be highly useful in collecting spectroscopic data at high temperatures particularly in the mid-infrared region.

Experimental temperature- and pressure-dependent absorbance cross sections and a pseudo-line-list model for methyl formate near [formula omitted]

We first present quantitative, broadband absorbance cross sections of the C=O stretch fundamental rovibrational band of methyl formate in the 1670–1850 cm−1 range at temperatures of 300, 600, 800, and 1000 K and pressures of 1–2 atm. The title molecular spectra were additionally studied across the pressure range of 1 to 35 atm at room temperature. Elevated temperature measurements were taken in argon bath gas behind the reflected shock wave of a shock tube by a rapid-tuning, broad-scan external cavity quantum cascade laser. The room temperature cross section of methyl formate was collected to validate our method and agreed well with previous room-temperature measurements by Sharpe et al. Then, to extend the utility of the collected data across intermediate temperatures, a pseudo-line-list (PLL) absorbance model was generated through a simultaneous fit of line-by-line intensities and lower-state energies to the measured cross sections. This PLL model was able to replicate the measurements within 3% across most of the spectral range and within 8% around the extremely sharp Q-branch feature present at room temperature. Cross-validation was then performed by re-fitting the PLL excluding the 800 K data set and demonstrated that the PLL approach is effective in interpolating between measured absorption cross sections at discrete temperatures. Finally, the additional room-temperature measurements from 1 to 35 atm were collected in a high-pressure static cell in nitrogen bath gas. These measurements revealed a notable Q-branch cross section pressure dependence while the P- and R-branch wings remained largely pressure independent across this wide pressure range. The collected methyl formate cross sections comprise the latest addition to the Stanford ShockGas-IR database for mid-infrared polyatomic absorption cross sections at elevated temperatures.

Two-photon absorption in bioactive C4-substituted Coumarin derivatives: Impact of electron-withdrawing and donating groups in different environment

The versatile applications of coumarin derivatives in materials processing, fluorescence imaging, data storage, and photodynamic therapy have sparked considerable interest in scientific community. In this research paper, we explore the UV–vis spectra, IR spectra, and two photon absorption (TPA) characteristics of biological active coumarin derivatives under the influence of electron withdrawing (specifically X = CONH2, CHO, and NO2) and electron donating (X= -CH3, -OH, -NH2) functional groups at C-4 position. To delve into the absorption spectra, we employ time-dependent density functional theory calculations. Results revealed that acceptor functional groups (specifically R = CONH2, CHO, and NO2) not only lower the energy of the lowest two photon active state but also increase the corresponding TPA cross-section. Furthermore, using the Conductor-like Polarizable Continuum Model (CPCM), the influence of solvent polarity on C-4 substituted coumarin derivative was also investigated. Our findings effectively capture how substitutions and solvents impact the nonlinear optical response in coumarins, as evidenced by the measurement of the two-photon absorption cross-section (σTPA). This study offers valuable insights for identifying and designing novel coumarin derivatives with C4 substitutions, unlocking new and intriguing possibilities for their practical applications.

Spectroscopic modeling and measurements of the CN Violet and Red systems for the development of nonequilibrium temperature and speciation diagnostics

The uniquely strong radiative properties of the cyano-radical (CN) make it an important species to model in high-enthalpy, nonequilibrium flows containing carbon and nitrogen. In this work, spectroscopic models for the Violet and Red systems of CN have been developed and validated at wavelengths in both the ultraviolet (UV) and near-infrared (NIR) regimes that would provide quantitative CN rovibrational temperature and concentration. The ultraviolet wavelengths chosen probe high-lying (J′′=30.5−40.5) and low-lying (J′′=0.5−5.5) rotational states in the ground vibrational level (v′′=0) of CN along with high-lying rotational states in the third excited vibrational level (v′′=3) of CN. Meanwhile, the NIR wavelengths cover a range of lower rovibrational content, including high-lying and low-lying rotational levels from the ground up to the fourth excited vibrational level of CN. Dilute cyanogen (C2N2) in argon (Ar) mixtures were shock heated to produce stable quantities of CN that could be spectroscopically studied. In the UV, fixed-temperature absorption cross-section measurements at different wavelengths and a fixed-wavelength temperature sweep for the chosen diagnostic wavelengths enabled an evaluation of the different spectroscopic models and their ability to correctly infer the post-shock temperature in mixtures with high Ar dilution. In the NIR, the lasers were scanned at 100 kHz to probe multiple transitions over different rovibrational states over a wide range of temperatures, and both Einstein A’s and relative line positions of observed Red transitions of CN were experimentally quantified.

A mid-IR laser diagnostic for HCN detection

Hydrogen cyanide (HCN) is a major source of prompt-NOx formation especially in fuel-bound nitrogen systems. To date, there is still a significant disagreement between experimental data and theoretical predictions of the rate coefficients of combustion reactions involving HCN as a prompt-NOx precursor. Accurate modeling of NOx formation would greatly benefit from a diagnostic capable of performing high-fidelity measurements of HCN formation/consumption time-histories. In this study, a laser diagnostic is developed for sensitive and selective HCN sensing by probing its most intense absorption feature in the mid-infrared (MIR). The diagnostic is based on difference-frequency generation (DFG) between a CO2 gas laser and an external-cavity quantum cascade laser in a nonlinear orientation-patterned gallium arsenide crystal which results in a DFG laser tunable over 11.56 − 15 µm. HCN measurements were carried out at the peak of the Q-branch of its strong ν2 vibrational band near 14 µm. Pressure dependence of the absorption cross-section was investigated at room temperature over the pressure range of 0.07 − 1.07 bar. Temperature-dependent absorption cross-section measurements were conducted behind reflected shock waves over the temperature range of 850 − 3000 K. The diagnostic was demonstrated in reactive experiments in a shock tube where HCN mole fraction time-histories were measured during the thermal decomposition of isoxazole (C3H3NO) and the first-order rate coefficients of C3H3NO → HCN + CH2CO reaction were determined.

Formation and consumption of HO2 radicals in ns pulse O2–He plasmas over a liquid water surface

Hydroperoxyl (HO2) radicals are an important precursor in the formation of hydrogen peroxide (H2O2), a key species in plasma-liquid interactions, such that their formation and consumption pathways need to be understood. In this work, the generation and decay of HO2 have been studied in a controlled environment, in ns pulse discharge O2–He plasmas in contact with a liquid water surface. For this, time-resolved, absolute number densities of HO2 in O2–He mixtures excited by a repetitive ns pulse discharge are measured in situ by cavity ring down spectroscopy (CRDS). The discharge cell with external electrodes to generate the plasma and a water reservoir are integrated into the CRDS cavity. The high-reflectivity cavity mirrors are purged with helium to protect them from water vapor condensation. The experimental results are obtained at near room temperature, both during the discharge pulse burst and in the afterglow. The HO2 number density is inferred from the CRDS data using a spectral model exhibiting good agreement with previous measurements of absolute HO2 absorption cross sections. HO2 is generated during the discharge burst and decays in the afterglow between the bursts. The HO2 number density is also measured vs. the O2 fraction in the mixture. Comparison with the kinetic modeling predictions demonstrates good agreement with the data and identifies the dominant HO2 generation and decay processes. HO2 in the plasma is formed predominantly by the recombination of H atoms, generated by the electron impact dissociation of water vapor, with O2 molecules. Reactions with O atoms and hydroxyl (OH) radicals are among the main HO2 decay processes in the afterglow. HO2 is also detected when O2 is not present in the mixture. In this case, it is generated primarily by the recombination of OH radicals, via the formation of H2O2. The results demonstrate that CRDS can also be used for HO2 and other plasma chemical reaction product measurements in atmospheric pressure plasma jets impinging on a liquid water surface in ambient air.

Linear and nonlinear absorption properties of hemicyanine dyes containing 5-(4H)-oxazolone as heterocyclic ring

A series of dyes containing electron-donating (D) and electron-accepting (A) groups connected through a π-conjugated linker were designed and their linear and nonlinear absorption properties were studied. The dyes combined 1,3-oxazol-5(4H)-one core with methoxy, methyl, phenyl, cyano, and nitro group in the para-position of a phenyl ring. Spectrally resolved two-photon absorption cross-section measurements carried out by the femtosecond Z-scan technique showed wide wavelength regions of nonlinear optical absorption. The studied compound containing the phenyl ring exhibits relatively high effective two-photon absorption cross-section equal to 772 ± 100 GM at 600 nm. The experimental optical characterization is supported by the results of electronic-structure calculations.

A laser-absorption sensor for in situ detection of biofuel blend vapor in engine intakes

A novel, mid-infrared laser-absorption sensor was developed for measurements of biofuel blend (E85) vapor in the intake runner of a single-cylinder internal combustion engine. The sensor used two mid-infrared interband cascade lasers to target a region of strong E85 absorbance near 3.35 µm. The lasers were co-aligned and fiber-coupled into the engine, and a two-color, online-offline differential absorption strategy was used to provide sensitive measurements of E85 vapor mole fraction and reject interference due to beam-steering and fuel droplet spray. An intensity-modulation spectroscopy (IMS) sensing scheme was employed to reject low-frequency additive noise and allow for frequency-domain multiplexing of the two lasers. High-resolution E85 absorption cross-section measurements were conducted in a static cell at a range of intake-relevant conditions. Validation experiments were performed in a laboratory setting to demonstrate sensor accuracy and noise rejection capability. The sensor was deployed on a single-cylinder development engine during dynamometer testing to provide time-resolved E85 vapor mole fraction measurements at a measurement rate of 40 kS/s, which corresponds to one measurement per crank angle degree at 6700 rpm. Time-resolved and average sensor measurements provide key performance insights for the development of intake systems in high-performance internal combustion engines.

Synthesis and optical properties of linear and branched styrylpyridinium dyes in different environments

A common motif in the design of organic dye compounds is that of an electron donor and an acceptor moiety linked through a conjugated bridge, but more complicated structures can also be built using such motifs as building blocks. Following these principles, we synthesized two styrylpyridinium dyes, a linear one and a branched molecule composed of three units of the mono moiety connected by benzyl group and investigated their photophysical properties in different environments: their linear absorption, one-photon excited fluorescence and two-photon absorption properties. The compound with the symmetrically substituted phenyl core shows a redshift of the absorption and fluorescence bands. Spectrally resolved two-photon absorption cross section measurements carried out by femtosecond Z-scan technique show that the value for the trimer is over twelve times larger than that for the monomer, and not just three times as expected from the molar mass increase. Large two-photon absorption (2PA) values were measured in the near infrared (NIR) region. The prototropic study indicates that the protonation of the amino group blocks a lone pair on the nitrogen atom, making the photoinduced electron transfer process from the amine group to the pyridinium ring ineffective. This results in the reduction of the long-wavelength absorption with a simultaneous increase of the band in the short-wavelength region of the spectrum and a decrease in the fluorescence intensity. The behavior of dyes in the presence of β-cyclodextrin was also studied based on NMR, UV–Vis, and fluorescence spectroscopy. The performed experiments indicated the formation of 1:1 inclusion complex in aqueous solution.

Time-resolved measurements of HO2 radical in a heated plasma flow reactor

Time-resolved, absolute HO2 number density in diluted H2O2-Ar, CH4O2-Ar, and C2H4O2-Ar mixtures excited by a repetitive ns pulse discharge in a heated plasma flow reactor is measured by Cavity Ringdown Spectroscopy (CRDS). The experimental results are obtained at T = 300–600 K and P = 130 Torr, both during the discharge pulse burst and in the afterglow. The HO2 number density is inferred from the CRDS data using a spectral model exhibiting good agreement with previous measurements of absolute HO2 absorption cross sections. In the room-temperature H2O2 mixture, as well as in CH4O2 and C2H4O2 mixtures over the entire temperature range studied, HO2 is generated only during the discharge burst and decays in the afterglow. However, in the H2O2 mixture at elevated temperatures, T = 400–600 K, HO2 persists in the afterglow up to 10 ms after the discharge burst, comparable with the flow residence time in the reactor. Comparison with kinetic modeling shows that the sustained reactivity after the source of radicals is turned off is due to a chain propagation/ hydrogen oxidation process, which dominates the radical recombination reactions. The kinetic modeling predictions are in good agreement with the relative HO2 number density measured in all three mixtures, although the model underpredicts the absolute number densities in H2O2 at T = 400–600 K by up to a factor of two. Detection of the sustained low-temperature reactivity in H2O2, initiated by the radical generation in the plasma, suggests that the plasma excitation may also affect kinetics of oxidation and reforming of fuels exhibiting low-temperature chemistry below hot ignition point.

Synthesis and Characterization of Atmospherically Relevant Hydroxy Hydroperoxides

Hydroxy hydroperoxides are formed upon OH oxidation of volatile organic compounds in the atmosphere and may contribute to secondary organic aerosol growth and aqueous phase chemistry after phase transfer to particles. Although the detection methods for oxidized volatile organic compounds improved much over the past decades, the limited availability of synthetic standards for atmospherically relevant hydroxy hydroperoxides prevented comprehensive investigations for the most part. Here, we present a straightforward improved synthetic access to isoprene-derived hydroxy hydroperoxides, i.e., 1,2-ISOPOOH and 4,3-ISOPOOH. Furthermore, we present the first successful synthesis of an α-pinene derived hydroxy hydroperoxide. All products were identified by 1H, 13C NMR spectroscopy for structure elucidation, additional 2D NMR experiments were performed. Furthermore, gas-phase FTIR- and UV/VIS spectra are presented for the first time. Using the measured absorption cross section, the atmospheric photolysis rate of up to 2.1 × 10−3 s−1 was calculated for 1,2-ISOPOOH. Moreover, we present the investigation of synthesized hydroxy hydroperoxides in an aerosol chamber study by online MS techniques, namely PTR-ToFMS and (NO3−)-CI-APi-ToFMS. Fragmentation patterns recorded during these investigations are presented as well. For the (NO3−)-CI-APi-ToFMS, a calibration factor for 1,2-ISOPOOH was calculated as 4.44 × 10−5 ncps·ppbv−1 and a LOD (3σ, 1 min average) = 0.70 ppbv.

Measurement of absorption cross sections of Co2+:MgAl2O4 crystals with transition of Co2+ ions along two orthogonal directions.

The nonlinear transmission curves of the Co2+:MgAl2O4 crystal at 1.5 µm are experimentally measured by the pump-probe technique. The measurement results demonstrate that the transition into the near-infrared absorption band is polarized not only along the C3 local symmetry axis, but also along the direction perpendicular to the C3 axis, arising from the distortion of oxygen tetrahedrons about the Co2+ ions along the four C3 local symmetry axes. The obtained saturation curves are analyzed using a theoretical model taking into account the transition of Co2+ ions along two orthogonal directions. The ground-state absorption cross sections for polarization parallel and perpendicular to the C3 axis are calculated to be 3.4×10-19cm2 and 2.6×10-20cm2, respectively. The excited-state absorption cross section for polarization parallel to the C3 axis is estimated to be4.2×10-20cm2.

Measurements of the water vapor continuum absorption by OFCEAS at 3.50 µm and 2.32 µm

Measurements of the water vapor absorption cross-sections at two spectral points of the 2.1 µm and 4.0 µm transparency windows are performed by optical feedback cavity enhanced absorption spectroscopy (OFCEAS).The self-continuum cross-section, CS, is measured for temperature values of 30 and 47°C (303 and 320 K) at the 2853 cm−1 spectral point, corresponding to the lowest opacity region of the 4.0 µm transparency window. The CS values derived from the pressure squared dependence of the self-continuum, are found consistent with previous CEAS measurements in the considered window but significantly smaller than measurements by Fourier transform spectroscopy (FTS). The CS temperature dependence is discussed in relation with FTS measurements at high temperature.Foreign-continuum cross-sections, CF, are newly obtained from OFCEAS spectra of moist air in flow regime at the 4302 cm−1 spectral point of the low energy edge of the 2.1 µm window. After subtraction of the monomer and self-continuum contributions, CF values are derived from the linear variation of the foreign-continuum absorption with the product of the water vapor and air partial pressures. The measurements were performed for temperature values of 34 and 47°C (307 and 320 K) and no significant temperature dependency was observed. The present CF value at 4302 cm−1 is gathered with previous CEAS measurements at seven spectral points of the 2.1 µm window. This consistent set of CF values is used to derive from a polynomial fit, the empirical frequency dependence of CF(ν) over the 4250-5000 cm−1 range. Overall, the semi-empirical MT_CKD_3.5 values of CF are significantly underestimated in the centre of the considered window.

Raman efficiency in the middle ultraviolet band for G‐series nerve agents and sulfur mustard

AbstractRaman spectroscopy has proven useful for chemical agent detection, but the wavelength‐dependent scattering cross section and absorption, as well as induced fluorescence, usually affects the sensitivity. Ultraviolet (UV) wavelength excitation is investigated as a method to increase the efficiency and possibly enhance the applicability for detection of contamination on surfaces from a distance, potentially including an imaging capability. With this aim, we have measured UV Raman spectra and their strength as a function of laser wavelength in a range from 210 to 330 nm using a tunable pulsed laser and a response calibrated spectroscopic system. Results from small droplets of the low volatile chemical warfare agents, GA (tabun), GF (cyclosarin), sulfur mustard (HD), and the agent simulant tributyl phosphate (TBP) applied to silicon wafer surfaces are reported. Particular emphasis is put on the radiative ratio of observed Raman scattering to laser excitation, quantified as the Raman target efficiency. Measured absorption cross sections were used to estimate the effective optical depth and molecular Raman cross sections as a function of wavelength. In addition, a secondary optical probe and spectrometer were used to monitor any induced fluorescence.

Spectrally-resolved absorption cross-section measurements of shock-heated [formula omitted] for the development of a vibrational temperature diagnostic

In shock-heated high-enthalpy air flows, the vibrational temperature of oxygen (O2) provides critical insight into the non-equilibrium chemistry. Here, a two-color O2 vibrational temperature diagnostic was developed by utilizing spectroscopic models to inform optimal wavelength candidates for both a continuous-wave (CW), ultraviolet (UV) laser and a picosecond pulsed, UV laser. Cross-sections of shock-heated O2 were measured using a CW UV laser, and results over a range of wavelengths and temperatures are compared against a Stanford model and Specair, a spectroscopic model for high temperature air species developed by Laux et al. All measurements were completed behind reflected shocks in 2% and 5% O2 in argon (Ar) mixtures. Vibrational temperatures for cross-section measurements were calculated for plateaus and peaks in experimental absorbances using a Bethe-Teller relaxation model up to 6,000 K and a steady-state approach above 6,000 K. Temperature sweep measurements were fixed around 223.237 nm, while wavelength sweep measurements were taken around 4550 K and ranged between 223.23 nm to 223.27 nm. Temperature sweep cross-sections agree to within 15% of Specair modeled cross-sections, with most measurements falling within 10% of Specair predictions. Wavelength sweep cross-sections agree at shorter wavelengths with Specair cross-sections, but longer wavelength features are offset from both the Stanford model and Specair predictions. Changing the spin-splitting equations used by the Stanford model from the Herzberg formulation to the Nicolet formulation also brought the Stanford model to within 15% of all temperature sweep data, with most measurements falling within 10% of the Stanford model predicts. The spin-splitting adjustment also improved the agreement between the Stanford model and the wavelength sweep data at shorter wavelengths.

Photoelectric absorption cross section of silicon near the bandgap from room temperature to sub-Kelvin temperature

The use of cryogenic silicon as a detector medium for dark matter searches is gaining popularity. Many of these searches are highly dependent on the value of the photoelectric absorption cross section of silicon at low temperatures, particularly near the silicon bandgap energy, where the searches are most sensitive to low mass dark matter candidates. While such cross section data have been lacking from the literature, previous dark matter search experiments have attempted to estimate this parameter by extrapolating it from higher temperature data. However, discrepancies in the high temperature data have led to order-of-magnitude differences in the extrapolations. In this paper, we resolve these discrepancies by using a novel technique to make a direct, low temperature measurement of the photoelectric absorption cross section of silicon at energies near the bandgap (1.2 eV–2.8 eV).

Absorption cross-section measurements of ortho-xylyl radical in the 460.1–475.1 nm region and investigation of its temperature and pressure dependence using cavity ringdown spectroscopy

The gas phase absorption cross-sections of o-xylyl radical were measured in the wavelength range of 460.1–475.1 nm with 0.2 nm resolution at 298 K and 40 Torr using pulsed laser photolysis-cavity ringdown spectroscopy (PLP-CRDS) and was found to be maximum at 468.3 nm [σo-xylyl468.3nm=(1.58 ± 0.38) × 10−18 cm2 molecule−1]. The temperature dependency of the cross-section was: σo-xylyl468.3nmT263-338K=[(6.39 ± 0.64) × 10−21] + [(2.60 ± 0.27) × 10−15 exp(−0.026 T/K)] cm2 molecule−1. A negligible pressure dependency was observed in the studied range of 40–95 Torr. The Time Dependent Density Functional Theory (TD-DFT) calculations were also performed to compute the visible absorption spectrum of o-xylyl radical.

Determination of gas-phase absorption cross-sections of FeO in a shock tube using intracavity absorption spectroscopy near 611 nm

We report state-resolved absorption cross-section measurement and oscillator-strength evaluation of the gas-phase iron oxide (FeO) orange system near 611 nm. Intracavity absorption spectroscopy (ICAS) with a homemade broadband dye laser was applied for time-resolved measurements of absorption spectra of shock-activated mixtures of iron pentacarbonyl and carbon dioxide (diluted in argon), generating gas-phase FeO. The measurements were performed with a time resolution of 170 µs in the spectral range of 16,316–16,353 cm−1 that includes a large number of FeO absorption lines. Across the 8-cm diameter of the shock tube, ICAS leads to an effective absorption path length of 260 m. Absorption cross-section values of 0.5 × 10–18–4 × 10–18 cm2 were determined for temperatures around 2200 K and pressures of ∼1.3 bar. Pressure- and temperature-independent oscillator strengths for individual ro-vibronic transitions within the 611-nm band of FeO orange system are reported for the first time. These data are generally applicable for quantitative absorption measurements of flame studies of iron chemistry, where FeO plays a key role as intermediate species.

Role of water vapour in the absorption of nanosecond 266-nm laser pulses by atmospheric air

The absorption of the Nd : YAG fourth harmonic in air and binary mixtures of water vapour with nitrogen and oxygen at atmospheric pressure has been measured as a function of pulse energy (peak intensity). The mixtures obtained by adding equal amounts of water vapour to dry nitrogen and oxygen have been found to differ significantly in absorption. Preliminary quantitative data have been obtained for two- and three-photon absorption cross sections of water and oxygen molecules: σ(2)(H2O) = (4 ± 1) ± 10–49 cm4 s and σ(3)(O2) = (5.6 ± 1.4) ± 10–78 cm6 s2. The absorption of 266-nm pulses with peak intensities from 0.05 to 2 GW cm–2 in the near-surface atmosphere has been shown to be determined by two-photon absorption in water vapour and three-photon absorption in oxygen. In moist air containing 1 % water vapour, the absorption coefficient for 266-nm laser pulses exceeds that in dry air by four to five times. There is no absorption in nitrogen. We have developed a technique for photoacoustic measurements of multiphoton absorption cross sections in single-component gases and gas mixtures.

Acetonyl Peroxy and Hydro Peroxy Self- and Cross-Reactions: Kinetics, Mechanism, and Chaperone Enhancement from the Perspective of the Hydroxyl Radical Product.

Pulsed laser photolysis coupled with infrared (IR) wavelength modulation spectroscopy and ultraviolet (UV) absorption spectroscopy was used to study the kinetics and branching fractions for the acetonyl peroxy (CH3C(O)CH2O2) self-reaction and its reaction with hydro peroxy (HO2) at a temperature of 298 K and pressure of 100 Torr. Near-IR and mid-IR lasers simultaneously monitored HO2 and hydroxyl, OH, respectively, while UV absorption measurements monitored the CH3C(O)CH2O2 concentrations. The overall rate constant for the reaction between CH3C(O)CH2O2 and HO2 was found to be (5.5 ± 0.5) × 10-12 cm3 molecule-1 s-1, and the branching fraction for OH yield from this reaction was directly measured as 0.30 ± 0.04. The CH3C(O)CH2O2 self-reaction rate constant was measured to be (4.8 ± 0.8) × 10-12 cm3 molecule-1 s-1, and the branching fraction for alkoxy formation was inferred from secondary chemistry as 0.33 ± 0.13. An increase in the rate of the HO2 self-reaction was also observed as a function of acetone (CH3C(O)CH3) concentration which is interpreted as a chaperone effect, resulting from hydrogen-bond complexation between HO2 and CH3C(O)CH3. The chaperone enhancement coefficient for CH3C(O)CH3 was determined to be kA″ = (4.0 ± 0.2) × 10-29 cm6 molecule-2 s-1, and the equilibrium constant for HO2·CH3C(O)CH3 complex formation was found to be Kc(R14) = (2.0 ± 0.89) × 10-18 cm3 molecule-1; from these values, the rate constant for the HO2 + HO2·CH3C(O)CH3 reaction was estimated to be (2 ± 1) × 10-11 cm3 molecule-1 s-1. Results from UV absorption cross-section measurements of CH3C(O)CH2O2 and prompt OH radical yields arising from possible oxidation of the CH3C(O)CH3-derived alkyl radical are also discussed. Using theoretical methods, no likely pathways for the observed prompt OH radical formation have been found and the prompt OH radical yields thus remain unexplained.