Cavity Ring-down Absorption Spectroscopy Research Articles

Cavity ring-down transient absorption spectroscopy (CRD-TAS): A proof of concept via detection of coherent artifacts of thin substrates

Cavity ring-down transient absorption spectroscopy (CRD-TAS): A proof of concept via detection of coherent artifacts of thin substrates

Nitrogen fixation in the stag beetle, Ceruchus piceus (Coleoptera: Lucanidae): could insects contribute more to ecosystem nitrogen budgets than previously thought?

Nitrogen (N) is a key nutrient required by all living organisms for growth and development, but is a limiting resource for many organisms. Organisms that feed on material with low N content, such as wood, might be particularly prone to N limitation. In this study, we investigated the degree to which the xylophagous larvae of the stag beetle Ceruchus piceus (Weber) use associations with N-fixing bacteria to acquire N. We paired acetylene reduction assays by cavity ring-down absorption spectroscopy (ARACAS) with 15N2 incubations to characterize rates of N fixation within C. piceus. Not only did we detect significant N fixation activity within C. piceus larvae, but we calculated a rate that was substantially higher than most previous reports for N fixation in insects. While taking these measurements, we discovered that N fixation within C. piceus can decline rapidly in a lab setting. Consequently, our results demonstrate that previous studies, which commonly keep insects in the lab for long periods of time prior to and during measurement, may have systematically under-reported rates of N fixation in insects. This suggests that within-insect N fixation may contribute more to insect nutrition and ecosystem-scale N budgets than previously thought.

Accurate measurement of trace H<sub>2</sub>S concentration based on cavity ring-down absorption spectroscopy under CO<sub>2</sub>/CO disturbance

Since H<sub>2</sub>S is a corrosive and toxic gas pollutant, the accurate measurement of its concentration is significant. However, in the practical industrial processes, it is difficult to implement because of the disturbance caused by other emissions such as CO<sub>2</sub> and CO. Therefore, in this work, the concentration of H<sub>2</sub>S, CO<sub>2</sub> and CO are measured simultaneously based on cavity ring-down spectroscopy (CRDS) as a viable alternative to measure the concentration of H<sub>2</sub>S accurately when CO<sub>2</sub> and CO exist. First, the wavelength of mixed gas within a range of 6336–6339 cm<sup>–1</sup> is selected as the target region where the spectral line intensity of H<sub>2</sub>S is stronger than 10 times that of CO<sub>2</sub> or CO and the water absorption is extremely weak. Second, the influence of the sampling length (Tm) on the accuracy of the ring-down time is analyzed by evaluating average (accuracy), standard deviation (precision) and consumption time (speed). Third, the experiments are carried out at different pressures in order to obtain the optimal pressure condition. Fourth, the concentration of trace H<sub>2</sub>S is measured when the disturbances caused by CO<sub>2</sub> or CO are added, and the error of the measured concentration is analyzed. Finally, the detection limit of CRDS-based system is calculated to be 6.9 ppb by analyzing the SNR of four groups of low concentration H<sub>2</sub>S spectra, while the lower limit of detection of CRDS-based system is calculated to be 2 ppb by analyzing the Allan variance of long-term data. The measured concentration and its desired value show a good linearity at different dilution ratios. Both the high linearity and the low detection limit of H<sub>2</sub>S indicate the effectiveness of the CRDS-based measurement system to measure H<sub>2</sub>S when CO<sub>2</sub> and CO exist. The successful application of the CRDS-based system to the measurement of H<sub>2</sub>S shows its promising prospect in gas concentration measurement for practical industrial processes.

In Vivo Temperature Dependency of Molybdenum and Vanadium Nitrogenase Activity in the Heterocystous Cyanobacteria Anabaena variabilis.

The reduction of atmospheric dinitrogen by nitrogenase is a key component of terrestrial nitrogen cycling. Nitrogenases exist in several isoforms named after the metal present within their active center: the molybdenum (Mo), the vanadium (V), and the iron (Fe)-only nitrogenase. While earlier in vitro studies hint that the relative contribution of V nitrogenase to total BNF could be temperature-dependent, the effect of temperature on in vivo activity remains to be investigated. In this study, we characterize the in vivo effect of temperature (3-42 °C) on the activities of Mo nitrogenase and V nitrogenase in the heterocystous cyanobacteria Anabaena variabilis ATTC 29413 using the acetylene reduction assay by cavity ring-down absorption spectroscopy. We demonstrate that V nitrogenase becomes as efficient as Mo nitrogenase at temperatures below 10-15 °C. At temperatures above 22 °C, BNF seems to be limited by O2 availability to respiration in both enzymes. Furthermore, Anabaena variabilis cultures grown in Mo or V media achieved similar growth rates at temperatures below 20 °C. Considering the average temperature on earth is 15 °C, our findings further support the role of V nitrogenase as a viable backup enzymatic system for BNF in natural ecosystems.

Probing BrCl from photodissociation of CH2BrCl and CHBr2Cl at 248 nm using cavity ring-down spectroscopy.

Photodissociation of di- and tri-halogenated methanes including CH2BrCl and CHBr2Cl at 248 nm was investigated using cavity ringdown absorption spectroscopy (CRDS). The spectra of the BrCl(v'' = 2, 3) and Br2(v'' = 1, 2) fragments were probed over the wavelength range of 594.5-596 nm in the B3Π+0u ← X1Σ+g and B3Π (0+) ← X1Σ+ transitions, respectively. Their corresponding spectra were simulated for assignment of rotational lines at a given vibrational level. The quantum yields for Br2 eliminated from CHBr2Cl and BrCl from CH2BrCl were determined to be 0.048 ± 0.018 and 0.037 ± 0.014, respectively. The photodissociation of CHBr2Cl yielded only the Br2 fragment, but not the BrCl fragment in the experiments. An ab initio theoretical method based on the CCSD(T)//B3LYP/6-311g(d,p) level was employed to evaluate the potential energy surface for the dissociation pathways to produce Br2 and BrCl from CHBr2Cl, which encountered a transition state barrier of 445 and 484 kJ mol-1, respectively. The corresponding RRKM rate constants were calculated to show that the branching ratio of (Br2/BrCl) is ∼20. The BrCl spectrum is expected to be obscured by the much larger Br2 spectrum, explaining why BrCl fragments cannot be detected in the photolysis of CHBr2Cl.

Photodissociation of CH2BrCHBrC(O)Cl at 248 nm: probing Br2 as the primary fragment using cavity ring-down spectroscopy.

The photodissociation of 2,3-dibromopropionyl chloride (CH2BrCHBrC(O)Cl, 2,3-DBPC) at 248 nm was carried out to study Br2 as the primary molecular product in the B3Π+0u ← X1Σ+g transition using cavity ring-down absorption spectroscopy. The rotational spectra (v'' = 0-2) were acquired and assigned with the aid of spectral simulation. It is verified that the obtained Br2 fragment is attributed to the one-photon dissociation of 2,3-DBPC and is free from contributions of secondary reactions. The vibrational ratio of the Br2 population of v(0):v(1):v(2) is equal to 1:(0.58 ± 0.12):(0.23 ± 0.09), corresponding to the Boltzmann vibrational temperature of 623 ± 38 K. The quantum yield of Br2 eliminated from 2,3-DBPC is estimated to be 0.09 ± 0.04. The dissociation pathways of 2,3-DBPC and its potential energy surfaces were calculated using density functional theory. By employing the CCSD(T)//M062X/6-31+g(d,p) level of theory, transition state barriers and corresponding reaction energies were calculated for the Br, Cl, Br2, BrCl, HBr and HCl elimination channels. The unimolecular rate constant for Br2 elimination was determined to be 2.09 × 105 s-1 using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, thus explaining the small quantum yield of the Br2 channel.

Optical cavity with intracavity two-photon absorption

This paper presents a theoretical analysis of the optical properties of an optical cavity with both one- and two-photon intracavity absorption loss, without saturation. The cavity two-photon absorption loss per pass is assumed to be small, but otherwise the analysis is general. Analytical results for the cavity transmission as a function of cavity parameters, linear and two-photon intracavity loss, and detuning from resonance are derived and limiting cases discussed. Extraction of the two-photon loss from both cavity ring-down and cavity-enhanced absorption spectroscopy methods is analyzed and the predicted shot-noise limited sensitivities derived and compared. Numerical results are computed using the parameters of a recent experimental intracavity measurement of two-photon absorption of nitrous oxide. The results will be useful in the design and interpretation of cavity-enhanced, two-photon absorption spectroscopy.

Photodissociation of CH2BrI using cavity ring-down spectroscopy: in search of a BrI elimination channel.

Photodissociation of CH2BrI was investigated in search of unimolecular elimination of BrI via a primary channel using cavity ring-down absorption spectroscopy (CRDS) at 248 nm. The BrI spectra were acquired involving the first three ground vibrational levels corresponding to A3Π1 ← X1Σ+ transition. With the aid of spectral simulation, the BrI rotational lines were assigned. The nascent vibrational populations for v'' = 0, 1, and 2 levels are obtained with a population ratio of 1 : (0.58 ± 0.10) : (0.34 ± 0.05), corresponding to a Boltzmann-like vibrational temperature of 713 ± 49 K. The quantum yield of the ground state BrI elimination reaction is determined to be 0.044 ± 0.014. The CCSD(T)//B3LYP/MIDI! method was employed to explore the potential energy surface for the unimolecular elimination of BrI from CH2BrI.

Cavity Ring-Down Absorption Spectroscopy: Optical Characterization of ICl Product in Photodissociation of CH2ICl at 248 nm.

Iodine monochloride (ICl) elimination from one-photon dissociation of CH2ICl at 248 nm is monitored by cavity ring-down absorption spectroscopy (CRDS). The spectrum of ICl is acquired in the transition of B3Π0 ← X1Σ+ and is confirmed to result from a primary photodissociation, that is, CH2ICl + hν → CH2 + ICl. The vibrational population ratio is determined with the aid of spectral simulation to be 1:(0.36 ± 0.10):(0.11 ± 0.05) for the vibrational levels ν = 0, 1, and 2 in the ground electronic state, corresponding to a Boltzmann-like vibrational temperature of 535 ± 69 K. The quantum yield of the ICl molecular channel for the reaction is obtained to be 0.052 ± 0.026 using a relative method in which the scheme CH2Br2 → CH2 + Br2 is adopted as the reference reaction. The ICl product contributed by the secondary collisions is minimized such that its quantum yield obtained is not overestimated. With the aid of the CCSD(T)//B3LYP/MIDI! level of theory, the ICl elimination from CH2ICl is evaluated to follow three pathways via either (1) a three-center transition state or (2) two isomerization transition states. However, the three-center concerted mechanism is verified to be unfavorable.

HO2 reaction kinetics in an atmospheric pressure plasma jet determined by cavity ring-down spectroscopy

Hydroperoxyl () is detected in the effluent of an atmospheric pressure plasma jet (PJ) by cavity ring-down absorption spectroscopy. Laser radiation at is used to determine concentrations directly in the plasma effluent at atmospheric pressure as well as indirectly after sampling through a pinhole and expanding to . To unravel the reaction kinetics, the argon feed gas is humidified and the PJ is equipped with a gas curtain device that controls the surrounding atmosphere. Varying the curtain gas composition from pure nitrogen to pure oxygen leads to a five to six-fold increase in concentrations towards higher oxygen concentrations. A reaction kinetics model considering near-field and far-field reactions describes the reaction pathways that determine the hydroperoxyl concentration and is in good agreement with the measurements at both low and atmospheric pressure.

Cl2 Elimination in 248 nm Photolysis of (COCl)2 Probed with Cavity Ring-Down Absorption Spectroscopy.

Cavity ring-down absorption spectroscopy (CRDS) is employed to investigate one-photon dissociation of (COCl)2 at 248 nm obtaining a primary Cl2 elimination channel. A ratio of vibrational population is estimated to be 1:(0.12 ± 0.03):(0.011 ± 0.003) for the v = 0, 1, and 2 levels. The quantum yield of Cl2 molecular channel is obtained to be 0.8 ± 0.4 initiated from the X̃1Ag ground state surface (COCl)2 via internal conversion. The obtained total quantum yield is attributed to both primary ((COCl)2 + hν → 2CO + Cl2) and secondary reactions (dominated by Cl + COCl → Cl2 + CO). The former is estimated to share a yield of >0.14, while the latter contributes up to 0.66. The photodissociation pathway to the molecular products is calculated to proceed via a four-center transition state (TS) from which Cl2 is eliminated synchronously. Installation of the mirrors with reflectivity of 99.995% in the CRDS apparatus prolongs the ring-down time to 70 μs, thus allowing for the contribution from 17% up to 66% of the total Cl2 yield from secondary reaction depending on the reaction temperature. Despite uncertainty in determining the product yield, the primary Cl2 dissociation channel eliminated from (COCl)2 is observed for the first time.

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH3)2COO.

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10-11 cm3 s-1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10-10 cm3 s-1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10-10 to (2.29 ± 0.08) × 10-10 cm3 s-1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10-12 cm3 s-1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s-1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.

Research and data processing of double locked cavity ringdown absorption spectroscopy

A continuous wave cavity ringdown spectroscopy based on a double-locking loop is proposed to improve the shortcoming of low acquisition rate of concentration in traditional scheme. A small portion of laser is separated to pass through a C2H2 reference cell, used to lock the laser frequency to the 1+3 band P(9)e absorption line of C2H2 at 6534.3634 cm-1 by the 1st harmonic demodulation of the frequency modulation spectroscopy. The remaining portion is incident on a high finesses cavity to observe the ringdown events. Meanwhile, the reflected light of cavity is used to extract the error signal to lock the laser based on the PDH frequency locking technique. As a consequence, the frequency drift of the laser and the jitter of the cavity length are improved, therefore a more relatively accuracy result is expected. The laser light is dual frequency modulated by a fiber coupled electro optic modulator (FEOM)in the above system. In order to optimize, to some extent, the asymmetry of the error signal caused by the residual amplitude modulation due to the inconsistency of the laser polarization direction with the extraordinary axis of the FEOM, the demodulation phase is adjusted carefully until the error signal is smoothed up and close to symmetry. Then, the effect of locking loop is examined. The frequency of laser, based on the measurement by a wavelength meter, is more stable and the relative frequency discrimination between the laser and the longitudinal mode of cavity is about 9.8 kHz. In addition, the PDH locking, ensuring the efficient coupling of the laser with the cavity, can gain a high acquisition rate of the concentration information. In order to obtain a complete ringdown event, the frequency of square wave to the fiber coupled acoustic optical modulator (FAOM) is limited to 30 kHz with the duty cycle of 85%, which is determined by the ringdown time and re-lock time. However, there exists a relatively large random noise in a series of ringdown time measurements of empty cavity, which is mainly caused by the errors of fitting and measurement. For the further improvement of the accuracy of experiment, an efficient digital filter, Kalman filter which can suppress the noise considerably at no expense of real-time capability, is used. The standard deviation of the ringdown time is reduced from 0.00333 to 0.00153. According to Allan variance analysis, the detection limit can reach 410-9 cm-1 for a 2 s integration time. Finally, the C2H2 gases with different concentrations from 100 ppb to 5 ppm are measured to demonstrate the linear response of this system.

Recombination of H+3 ions with electrons in He/H2 ambient gas at temperatures from 240 K to 340 K

We have studied the recombination of ions with electrons in a stationary afterglow experiment either in pure hydrogen or in mixtures of helium, hydrogen, and argon. The decay of the ion density during the afterglow was monitored using near-infrared cavity ring-down absorption spectroscopy. The gas temperatures ranged from 240 K to 340 K. We find that three-body recombination, where molecular hydrogen acts as a third body, increases the recombination rate significantly. However, assisted three-body recombination saturates at hydrogen densities above and the recombination rate then becomes nearly independent of the neutral gas density. The saturation can lead to the erroneous conclusion that the recombination is purely binary and this appears to be the cause of some inconsistencies between previously reported recombination rate coefficients. At temperatures 240–340 K the obtained three-body recombination rate coefficient is independent on temperature () and it is larger by five orders of magnitude than those expected from the classical theory for atomic ions of Bates and Khare (). The observed dependences on density suggest that a substantial fraction of neutral complexes formed in capture of electrons by ions do not rapidly predissociate but can be stabilized by interactions with third bodies. Saturation occurs if the capture step is rate limiting rather than stabilization.

Cavity Ring Down Spectroscopy Measurements for High-Overtone Vibrational Bands of HC3N.

Overtone (5ν1 and 6ν1) and combination (4ν1 + ν3 and 4ν1 + ν2) vibrational bands of gaseous HC3N, located in the visible range (14,600-15,800 and 17,400-18,600 cm(-1)), were investigated by cavity ring-down absorption spectroscopy. The 5ν1 + ν3 and 5ν1 + ν2 combinations as well as the 6ν1 + ν5 - ν5 hot overtone band have also been identified, on the basis of previous overtone assignments. Absolute integrated intensity values and the ensuing oscillator strengths have been measured here for the first time; f values are typically confined between 4 × 10(-12) and 7 × 10(-11). For the even weaker 5ν1 + ν2 combination band, the oscillator strength was estimated as 9 × 10(-13). The values concerning CH-stretch overtones (nν1) are similar to those found in the literature for HCN and C2H2, the molecules with sp-hybridized carbon atoms. Data presented here may prove useful for studying the photochemistry triggered with visible or near-IR radiation within the atmospheres of certain Solar System bodies, including Titan.

Characterization of molecular channel in photodissociation of SOCl2 at 248 nm: Cl2 probing by cavity ring-down absorption spectroscopy.

A primary elimination channel of the chlorine molecule in the one-photon dissociation of SOCl2 at 248 nm was investigated using cavity ring-down absorption spectroscopy (CRDS). By means of spectral simulation, the ratio of the vibrational population in the v = 0, 1, and 2 levels was evaluated to be 1 : (0.10 ± 0.02) : (0.009 ± 0.005), corresponding to a Boltzmann vibrational temperature of 340 ± 30 K. The Cl2 molecular channel was obtained with a quantum yield of 0.4 ± 0.2 from the X(1)A' ground state of SOCl2via internal conversion. The dissociation mechanism differs from a prior study where a smaller yield of <3% was obtained, initiated from the 2(1)A' excited state. Temperature-dependence measurements of the Cl2 fragment turn out to support our mechanism. With the aid of ab initio potential energy calculations, two dissociation routes to the molecular products were found, including one synchronous dissociation pathway via a three-center transition state (TS) and the other sequential dissociation pathway via a roaming-mediated isomerization TS. The latter mechanism with a lower energy barrier dominates the dissociation reaction.

Detection of vibronic bands of C3 in a translucent cloud towards HD 169454

We report the detection of eight vibronic bands of C3, seven of which have been hitherto unobserved in astrophysical objects, in the translucent cloud towards HD 169454. Four of these bands are also found towards two additional objects: HD 73882 and HD 154368. Very high signal-to-noise ratio (∼1000 and higher) and high resolving power (R = 80 000) UVES-VLT spectra (Paranal, Chile) allow for detecting novel spectral features of C3, even revealing weak perturbed features in the strongest bands. The work presented here provides the most complete spectroscopic survey of the so far largest carbon chain detected in translucent interstellar clouds. High-quality laboratory spectra of C3 are measured using cavity ring-down absorption spectroscopy in a supersonically expanding hydrocarbon plasma, to support the analysis of the identified bands towards HD 169454. A column density of N(C3) = (6.6 ± 0.2) × 1012 cm−2 is inferred and the excitation of the molecule exhibits two temperature components; Texc = 22 ± 1 K for the low-J states and Texc = 187 ± 25 K for the high-J tail. The rotational excitation of C3 is reasonably well explained by models involving a mechanism including inelastic collisions, formation and destruction of the molecule, and radiative pumping in the far-infrared. These models yield gas kinetic temperatures comparable to those found for Texc. The assignment of spectral features in the UV-blue range 3793–4054 Å may be of relevance for future studies aiming at unravelling spectra to identify interstellar molecules associated with the diffuse interstellar bands (DIBs).

DNA interaction probed by evanescent wave cavity ring-down absorption spectroscopy via functionalized gold nanoparticles

Evanescent wave cavity ring-down absorption spectroscopy (EW-CRDS) is employed to study interaction and binding kinetics of DNA strands by using gold nanoparticles (Au NPs) as sensitive reporters. These Au NPs are connected to target DNA of study that hybridizes with the complementary DNA fixed on the silica surface. By the absorbance of Au NPs, the interaction between two DNA strands may be examined to yield an adsorption equilibrium constant of 2.2×1010M−1 using Langmuir fit. The binding efficiency that is affected by ion concentration, buffer pH and temperature is also examined. This approach is then applied to the label-free detection of the DNA mutation diseases using the sandwich hybridization assay. For monitoring a gene associated with sickle-cell anemia, the detection limit and the adsorption equilibrium constant is determined to be 1.2pM and (3.7±0.8)×1010M−1, distinct difference from the perfectly matched DNA sequence that yields the corresponding 0.5pM and (1.1±0.2)×1011M−1. The EW-CRDS method appears to have great potential for the investigation of the kinetics of a wide range of biological reactions.

Molecular halogen elimination from halogen-containing compounds in the atmosphere

Atmospheric halogen chemistry has drawn much attention, because the halogen atom (X) playing a catalytic role may cause severe stratospheric ozone depletion. Atomic X elimination from X-containing hydrocarbons is recognized as the major primary dissociation process upon UV-light irradiation, whereas direct elimination of the X2 product has been seldom discussed or remained a controversial issue. This account is intended to review the detection of X2 primary products using cavity ring-down absorption spectroscopy in the photolysis at 248 nm of a variety of X-containing compounds, focusing on bromomethanes (CH2Br2, CF2Br2, CHBr2Cl, and CHBr3), dibromoethanes (1,1-C2H4Br2 and 1,2-C2H4Br2) and dibromoethylenes (1,1-C2H2Br2 and 1,2-C2H2Br2), diiodomethane (CH2I2), thionyl chloride (SOCl2), and sulfuryl chloride (SO2Cl2), along with a brief discussion on acyl bromides (BrCOCOBr and CH2BrCOBr). The optical spectra, quantum yields, and vibrational population distributions of the X2 fragments have been characterized, especially for Br2 and I2. With the aid of ab initio calculations of potential energies and rate constants, the detailed photodissociation mechanisms may be comprehended. Such studies are fundamentally important to gain insight into the dissociation dynamics and may also practically help to assess the halogen-related environmental variation.

Molecular elimination of Br2 in photodissociation of CH2BrC(O)Br at 248 nm using cavity ring-down absorption spectroscopy

The primary elimination channel of bromine molecule in one-photon dissociation of CH(2)BrC(O)Br at 248 nm is investigated using cavity ring-down absorption spectroscopy. By means of spectral simulation, the ratio of nascent vibrational population in v = 0, 1, and 2 levels is evaluated to be 1:(0.5 ± 0.1):(0.2 ± 0.1), corresponding to a Boltzmann vibrational temperature of 581 ± 45 K. The quantum yield of the ground state Br(2) elimination reaction is determined to be 0.24 ± 0.08. With the aid of ab initio potential energy calculations, the obtained Br(2) fragments are anticipated to dissociate on the electronic ground state, yielding vibrationally hot Br(2) products. The temperature-dependence measurements support the proposed pathway via internal conversion. For comparison, the Br(2) yields are obtained analogously from CH(3)CHBrC(O)Br and (CH(3))(2)CBrC(O)Br to be 0.03 and 0.06, respectively. The trend of Br(2) yields among the three compounds is consistent with the branching ratio evaluation by Rice-Ramsperger-Kassel-Marcus method. However, the latter result for each molecule is smaller by an order of magnitude than the yield findings. A non-statistical pathway so-called roaming process might be an alternative to the Br(2) production, and its contribution might account for the underestimate of the branching ratio calculations.