Cavity Ring-down Absorption Research Articles

Absolute OH and O radical densities in effluent of a He/H2O micro-scaled atmospheric pressure plasma jet

The effluent of a micro-scaled atmospheric pressure plasma jet (μ-APPJ) operated in helium with admixtures of water vapor ( ppm) has been analyzed by means of cavity ring-down laser absorption spectroscopy and molecular beam mass spectrometry to measure hydroxyl (OH) radical densities, and by two-photon absorption laser-induced fluorescence spectroscopy to measure atomic oxygen (O) densities. Additionally, the performance of the bubbler as a source of water vapor in the helium feed gas has been carefully characterized and calibrated. The largest OH and O densities in the effluent of and , respectively, have been measured at around 6000 ppm. The highest selectivity is reached around 1500 ppm, where the OH density is at ∼63% of its maximum value and is 14 times larger than the O density. The measured density profiles and distance variations are compared to the results of a 2D axially symmetric fluid model of species transport and reaction kinetics in the plasma effluent. It is shown that the main loss of OH radicals in the effluent is their mutual reaction. In the case of O, reactions with other species than OH also have to be considered to explain the density decay in the effluent. The results presented here provide additional information for understanding the plasma-chemical processes in non-equilibrium atmospheric pressure plasmas. They also open the way to applying μ-APPJ with He/H2O as a selective source of OH radicals.

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.

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of δ18O and δ2H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature (Tair), with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial–temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world.

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.

Lowest triplet $ {\bm ( n , \pi ^* )}$(n,π*) state of 2-cyclohexen-1-one: Characterization by cavity ringdown spectroscopy and quantum-chemical calculations

The cavity ringdown (CRD) absorption spectrum of 2-cyclohexen-1-one (2CHO) was recorded over the range 401.5-410.5 nm in a room-temperature gas cell. The very weak band system (ε ≤ 0.1 M(-1) cm(-1)) in this spectral region is due to the T1(n, π*) ← S0 electronic transition. The 0(0)(0) origin band was assigned to the feature observed at 24,558.8 ± 0.3 cm(-1). We have assigned 46 vibronic transitions in a region extending from -200 to +350 cm(-1) relative to the origin band. For the majority of these transitions, we have made corresponding assignments in the spectrum of the deuterated derivative 2CHO-2,6,6-d3. From the assignments, we determined fundamental frequencies for several vibrational modes in the T1(n, π*) excited state of 2CHO, including the lowest ring-twisting (99.6 cm(-1)) and ring-bending (262.2 cm(-1)) modes. These values compare to fundamentals of 122.2 cm(-1) and 251.9 cm(-1), respectively, determined previously for the isoconfigurational S1(n, π*) excited state of 2CHO and 99 cm(-1) and 248 cm(-1), respectively, for the S0 ground state. With the aid of quantum-mechanical calculations, we have also ascertained descriptions for these two modes, thereby resolving ambiguities appearing in the previous literature. The ring-twisting mode (ν39) contains a significant contribution from O=C-C=C torsion, whereas the ring-bending mode (ν38 in the ground state) involves mainly the motion of C-5 with respect to the plane containing the other heavy atoms. The CRD spectroscopic data for the T1(n, π*) state have allowed us to benchmark several computational methods for treating excited states, including time-dependent density functional theory and an equation-of-motion coupled cluster method. In turn, the computational results provide an explanation for observed differences in the T1(n, π*) vs. S1(n, π*) ring frequencies.

Evaluation of the use of a commercially available cavity ringdown absorption spectrometer for measuring NO2 in flight, and observations over the Mid-Atlantic States, during DISCOVER-AQ

Real time, atmospheric NO2 column profiles over the Mid-Atlantic states, during the July 2011 National Aeronautics and Space Administration (NASA) Deriving Information on Surface Conditions from Column and Vertically Resolved Observations to Air Quality (DISCOVER AQ) flight campaign, demonstrated that a cavity ring down spectrometer with a light emitting diode light source (LED-CRD) is a suitable technique for detecting NO2 in the boundary layer (BL) and lower free troposphere (LFT). Results from a side-by-side flight between a NASA P3 aircraft and a University of Maryland (UMD) Cessna 402B aircraft show that NO2 concentrations in ambient air from 0.08 nmol /mol (or ppbv) to 1.3 nmol/mol were consistent with NO2 measurements obtained via laser induced fluorescence (LIF) and photolysis followed by NO chemiluminescence (P-CL). The current LED-CRD, commercially available by Los Gatos Research (LGR), includes the modifications added by Castellanos et al. (Rev. Sci. Instrum. 80:113107, 2009) to compensate for baseline drift and humidity through built in zeroing and drying. Because of laser instability in the initial instrument, the laser light source in the Castellanos et al. (Rev. Sci. Instrum. 80:113107, 2009) instrument has been replaced with a light emitting diode. Six independent calibrations demonstrated the instrument’s linearity up through 150 nmol/mol NO2 and excellent stability in calibration coefficient of 1.26 (± 3.7 %). The instrument detection limit is 80 pmol/mol. Aircraft measurements over the Mid-Atlantic are included showing horizontal and vertical distributions of NO2 during air quality episodes. During 23 research flights, NO2 profiles were measured west and generally upwind of the Baltimore/Washington, D.C. area in the morning and east (generally downwind) of the metropolitan region in the afternoon. Column contents (surface to 2,500 m altitude) were remarkably similar (≈3 × 1015 molecules/cm2) indicating that NO2 is widely distributed over the eastern US contributing to the regional (spatial scales of approximately1000 km) nature of smog events.

Monitoring water stable isotopic composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy

[1] In soils, the isotopic composition of water (δ2H and δ18O) provides qualitative (e.g., location of the evaporation front) and quantitative (e.g., evaporation flux and root water uptake depths) information. However, the main disadvantage of the isotope methodology is that contrary to other soil state variables that can be monitored over long time periods, δ2H and δ18O are typically analyzed following destructive sampling. Here we present a nondestructive method for monitoring soil liquid water δ2H and δ18O over a wide range of water availability conditions and temperatures by sampling water vapor equilibrated with soil water using gas-permeable polypropylene tubing and a cavity ring-down laser absorption spectrometer. By analyzing water vapor δ2H and δ18O sampled with the tubing from a fine sand for temperatures ranging between 8°C and 24°C, we demonstrate that our new method is capable of monitoring δ2H and δ18O in soils online with high precision and after calibration, also with high accuracy. Our sampling protocol enabled detecting changes of δ2H and δ18O following nonfractionating addition and removal of liquid water and water vapor of different isotopic compositions. Finally, the time needed for the tubing to monitor these changes is compatible with the observed variations of δ2H and δ18O in soils under natural conditions.

Absorption Measurements in Liquid Core Waveguides Using Cavity Ring-Down Spectroscopy

Short liquid core waveguides (LCWs) were included into a fiber-loop cavity ring-down absorption spectrometer to reduce the detection limit over, both, single pass absorption in a LCW and cavity-enhanced absorption using a conventional fiber-loop cavity. LCWs of 5 and 10 cm length were interfaced with a pressure-flow system and a multimode fiber-loop cavity using concave fiber lenses with matching numerical apertures and diameters. Two red dyes, Allura Red AC and Congo Red, were detected with a 532 nm pulsed laser at a 5 nM limit of detection in a detection volume of less than 1 μL, corresponding to a minimal detectable absorbance of less than 4 × 10(-4) cm(-1) and a minimal detectable change in absorption cross section, σ(min) = V(det) × ε × C(LOD), of about 14 μm(2) (Allura Red AC) and 37 μm(2) (Congo Red).

Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

The cavity ringdown absorption spectrum of acrolein (propenal, CH(2)=CH-CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0(0)(0) band of the T(1)(n, π*) ← S(0) system. We analyzed the 0(0)(0) rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T(1)(n, π*) inertial constants to the room-temperature contour. The determined values (cm(-1)), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T(1)(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T(1)(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)] used a triple zeta-quality basis set to optimize the T(1)(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial constants, while the economical unrestricted Perdew-Burke-Ernzerhof exchange-correlation hybrid functional (UPBE0) technique performs nearly as well.

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.

Binary and ternary recombination of ${\rm D}_3^+$D3+ ions at 80–130 K: Application of laser absorption spectroscopy

Recombination of D(3)(+) ions with electrons at low temperatures (80-130 K) was studied using spectroscopic determination of D(3)(+) ions density in afterglow plasmas. The use of cavity ring-down absorption spectroscopy enabled an in situ determination of the abundances of the ions in plasma and the translational and the rotational temperatures of the recombining ions. Two near infrared transitions at (5792.70 ± 0.01) cm(-1) and at (5793.90 ± 0.01) cm(-1) were used to probe the number densities of the lowest ortho state and of one higher lying rotational state of the vibrational ground state of D(3)(+) ion. The results show that D(3)(+) recombination with electrons consists of the binary and the third-body (helium) assisted process. The obtained binary recombination rate coefficients are in agreement with a recent theoretical prediction for electron-ion plasma in thermodynamic equilibrium with α(bin)(80 K) = (9.2 ± 2.0) × 10(-8) cm(3) s(-1). The measured helium assisted ternary rate coefficients K(He) are in agreement with our previously measured flowing afterglow data giving a value of K(He)(80 K) = (1.2 ± 0.3) × 10(-25) cm(6) s(-1).

Three-level depletion by cavity ringdown absorption spectroscopy: proof of concept

Theoretical quantitative considerations as well as experimental data are presented based on absorption population depletion coupled with cavity ringdown spectroscopy. The absorbing number densities inside the cavity are determined by numerical integration of the coupled rate equations. The number of photons involved in absorption, cavity losses due to mirror reflectivity and stimulated emission are taken into account. The principle is to monitor a first transition by cavity ringdown spectroscopy while a second transition, with a state in common, is resonantly excited by the decaying radiation of different frequency also trapped inside the optical cavity. A numerical example is given for atomic lines of neon and the measurements carried out in a supersonic slit-jet expansion discharge demonstrate the feasibility of the technique. The technique is also proven to work with two resonant transitions of C2. Translational velocity of the jet modifying the rate equations is included in the model.

Short-Term N2 Fixation Kinetics in a Moss-Associated Cyanobacteria

N(2) fixation by moss-associated cyanobacteria plays an important role in the nitrogen cycling of terrestrial ecosystems. Recent studies have mainly focused on boreal ecosystems; little is known about such association in other ecosystems. Moss-associated cyanobacteria are subject to rapid changes (hourly or less) in environmental conditions that may affect N(2) fixation kinetics. Using a recently developed method (Acetylene Reduction Assays by Cavity ring-down laser Absorption Spectroscopy, ARACAS) with higher sensitivity and sampling frequency than the conventional method, we characterize short-term kinetics of N(2) fixation by cyanobacteria on moss carpets from warm and cold temperate forests. We report the identification of a heretofore unknown multispecies true-moss-cyanobacteria diazotrophic association. We demonstrate that short-term change in abiotic variables greatly influences N(2) fixation. We also show that difference in relative proportion of two epiphytic diazotrophs is consistent with divergent influences of temperature on their N(2) fixation kinetics. Further research is needed to determine whether this difference is consistent with a latitudinal trend.

Binary and ternary recombination of para-${\rm H}_3^+$H3+ and ortho-${\rm H}_3^+$H3+ with electrons: State selective study at 77–200 K

Measurements in H(3)(+) afterglow plasmas with spectroscopically determined relative abundances of H(3)(+) ions in the para-nuclear and ortho-nuclear spin states provide clear evidence that at low temperatures (77-200 K) para-H(3)(+) ions recombine significantly faster with electrons than ions in the ortho state, in agreement with a recent theoretical prediction. The cavity ring-down absorption spectroscopy used here provides an in situ determination of the para/ortho abundance ratio and yields additional information on the translational and rotational temperatures of the recombining ions. The results show that H(3)(+) recombination with electrons occurs by both binary recombination and third-body (helium) assisted recombination, and that both the two-body and three-body rate coefficients depend on the nuclear spin states. Electron-stabilized (collisional-radiative) recombination appears to make only a small contribution.

What Is the Best DFT Functional for Vibronic Calculations? A Comparison of the Calculated Vibronic Structure of the S1–S0 Transition of Phenylacetylene with Cavity Ringdown Band Intensities

The sensitivity of vibronic calculations to electronic structure methods and basis sets is explored and compared to accurate relative intensities of the vibrational bands of phenylacetylene in the S(1)(A(1)B(2)) ← S(0)(X(1)A(1)) transition. To provide a better measure of vibrational band intensities, the spectrum was recorded by cavity ringdown absorption spectroscopy up to energies of 2000 cm(-1) above the band origin in a slit jet sample. The sample rotational temperature was estimated to be about 30 K, but the vibrational temperature was higher, permitting the assignment of many vibrational hot bands. The vibronic structure of the electronic transition was simulated using a combination of time-dependent density functional theory (TD-DFT) electronic structure codes, Franck-Condon integral calculations, and a second-order vibronic model developed previously [Johnson, P. M.; Xu, H. F.; Sears, T. J. J. Chem. Phys. 2006, 125, 164331]. The density functional theory (DFT) functionals B3LYP, CAM-B3LYP, and LC-BLYP were explored. The long-range-corrected functionals, CAM-B3LYP and LC-BLYP, produced better values for the equilibrium geometry transition moment, but overemphasized the vibronic coupling for some normal modes, while B3LYP provided better-balanced vibronic coupling but a poor equilibrium transition moment. Enlarging the basis set made very little difference. The cavity ringdown measurements show that earlier intensities derived from resonance-enhanced multiphoton ionization (REMPI) spectra have relative intensity errors.