Approximated Uncertainty Propagation of Correlated Independent Variables Using the Ordinary Least Squares Estimator.

For chemical measurements, calibration is typically conducted by regression analysis. In many cases, generalized approaches are required to account for a complex-structured variance-covariance matrix of (in)dependent variables. However, in the particular case of highly correlated independent variables, the ordinary least squares (OLS) method can play a rational role with an approximated propagation of uncertainties of the correlated independent variables into that of a calibrated value for a particular case in which standard deviation of fit residuals are close to the uncertainties along the ordinate of calibration data. This proposed method aids in bypassing an iterative solver for the minimization of the implicit form of the squared residuals. This further allows us to derive the explicit expression of budgeted uncertainties corresponding to a regression uncertainty, the measurement uncertainty of the calibration target, and correlated independent variables. Explicit analytical expressions for the calibrated value and associated uncertainties are given for straight-line and second-order polynomial fit models for the highly correlated independent variables.

Photochemical Reaction Mechanism of Intramolecular H Transfer Reaction of H2 C3 O+ ⋠Radical Cation.

The photochemical reaction mechanism underlying the intramolecular H-transfer of the H2 C3 O+ ⋅ radical cation to the H2 CCCO+ ⋅ methylene ketene cation was elucidated using time-dependent density functional theory and high-level ab initio methods. Once the D1 state of H2 C3 O+ ⋅ is populated, the reaction proceeds to form an intermediate (IM) in the D1 state (IM4D1 ). The molecular structure of the conical intersection (CI) was optimized using a multiconfigurational ab initio method. The CI is readily accessible because it lies slightly above the IM4D1 in energy. In addition, the gradient difference vector of the CI is almost parallel to the intramolecular H-transfer reaction coordinate. Once the vibration mode of IM4D1 which is parallel to the reaction coordinate is populated, the degeneracy of the CI is readily lifted and H2 CCCO+ ⋅ was formed via a relaxation pathway in the D0 state. Our calculated results clearly describe the photochemical intramolecular H transfer reaction reported in a recent study.

Multi-Gas Analyzer Based on Tunable Filter Non-Dispersive Infrared Sensor: Application to the Monitoring of Eco-Friendly Gas Insulated Switchgears.

This study presents a multi-gas analyzer based on tunable filter non-dispersive IR (TF-NDIR) sensors that operate with a wide dynamic range of wavelength and concentration. A pyroelectric sensor coupled with a microsized Fabry-Perot interferometer, namely a tunable filter, enables sensing within a narrowly selected wavelength band. Three detectors capable of tuning the bandpass wavelength with a range of 3.8-5.0 µm, 5.5-8.0 µm, and 8.0-10.5 µm are combined to encompass the entire mid-IR region. single-pass cell with an optical path length (OPL) of 5 cm and a multi-pass cell with an OPL of 10.5 m is selected to encompass a concentration range from ppmv to percent. The TF-NDIR sensors and gas cells can be reconfigured by manipulating the beam path. A homemade lock-in amplifier is used to enhance the signal-to-noise ratio 88 times greater than that of the bare signal. The performance of the gas analyzer is evaluated by measuring the SF6 and Novec-4710/CO2 mixture, which are the dielectric gas medium for a gas-insulated switch (GIS). The mixing ratio of the Novec-4710/CO2 mixture is measured within a range of 3-7% using premixes. The measurement precision is 0.72% for 0.5 s. Trace level measurements of Novec-4710, CO2, SF6, which are measurands for detecting gas leakage from the GIS, CO, and SO2 which are measurands for detecting product generated by the arc or thermal decomposition in the switching electrode, are conducted based on dynamic partial pressure adjustment using 1000 ppmv mother premixes in N2. The limit of detection is 54.7 ppmv for Novec-4710, 112.8 ppmv for CO, 118.1 ppmv for CO2, 69.5 ppmv for SO2, and 33.5 ppmv for SF6.

Detachable Trap Preconcentrator with a Gas Chromatograph-Mass Spectrometer for the Analysis of Trace Halogenated Greenhouse Gases.

A detachable trap preconcentrator coupled with a gas chromatograph-mass spectrometer (GC-MS) was developed for measuring trace amounts of anthropogenic halogenated greenhouse gases such as hydrofluorocarbons (HFCs) and nitrogen trifluoride (NF3). Hayesep D cooled to -135 °C was used as an adsorbent for preconcentrating the target analytes. A differential trapping method was applied to remove major interfering substances such as CO2, N2, and O2 in order to ensure sufficient sampling volume of secondary injection trap. This was accomplished without using any CO2-removal agent such as molecular sieve adsorbents. Consequently, the temperature of the primary transfer trap was set to -75 °C for selective desorption of a significant amount of CO2 that could be vented out. In the meantime, the major components of air, e.g., N2 and O2, were vented out before transferring the analytes to the secondary injection trap, in order to protect the gas plumbing from pressure shock induced by rapid temperature ramping over 100 °C/min in the secondary trap. When the traps were heated, linear motion was operated to detach them from the copper baseplate on the freezer, thereby restricting heat transfer to the freezer and maintaining the freezer close to the background temperature of -135 °C. This trap design is a key improvement to address the insufficient cooling capacity of the employed freezer, allowing sensitive detection of trace halogenated greenhouse gases in GC-MS. NF3 and various HFCs at ambient levels were quantitatively and qualitatively measured with a precision of 0.35% at rates below 45 min/cycle. In particular, the limit of detection for NF3 was evaluated to be 0.2 pmol/mol, with linear responses at ambient concentration.

Gravimetric Standard Gas Mixtures for Global Monitoring of Atmospheric SF6.

In this study, standard gas mixtures of SF6 in synthetic air were gravimetrically developed as a suite consisting of 6 mixtures with mole fractions of SF6 ranging from 5 to 15 pmol/mol. For precision in weighing the gas fills, an automatic weighing system coupled with a high sensitivity mass balance was used and a gravimetry precision of 3 mg (2σ) was achieved. Impurity profiles of the raw gases were determined by various analyzers. In particular, sub pmol/mol levels of SF6 in the matrix components (N2, O2, and Ar) were carefully measured, since the mole fraction of SF6 in the final step can be significantly biased by this trace amount of SF6 in the raw gases of the matrix components. Gravimetric dilution of SF6 by purity-assessed N2 was performed in 6 steps to achieve a mole fraction of 440 pmol/mol. In the final step, O2 and Ar were added to mimic the atmospheric composition. Gravimetric fractions of SF6 and the associated standard uncertainty in each step were computed according to the ISO 6142 and JCGM 100:2008, respectively, and validated experimentally. Eventually, the SF6 fraction uncertainty of the standard gas mixtures combined by uncertainties of gravimetric preparation and verification measurements were found to be nominally 0.08% at a 95% confidence interval. A comparison with independent calibration standards from NOAA shows agreement within 0.49%, satisfying the extended WMO compatibility goal, 0.05 ppt.

Theoretical Investigation of the Reaction Mechanism of the Photoisomerization of 1,2-Dihydro-1,2-azaborine.

The photoisomerization of 1,2-dihydro-1,2-azaborine was investigated by high-level multireference ab initio and density functional theory calculations. The intermediates (IMs) and transition states (TSs) on the S(0) and S(1) states were optimized using the state-averaged complete active space self-consistent field method. The multireference configuration interaction method with the Davidson correction was used to obtain accurate energetics. Moreover, the conical intersections (CIs), which play a crucial role in photoisomerization, were also optimized. On the basis of the calculation results, the most favorable proposed reaction pathway is as follows: reactant→Franck-Condon region→TS(1) →CI→IM(0) →TS(0P) →product. The product was not directly formed through the CI, and the IM(0) existed on the S(0) state. These results show that the isomerization of 1,2-dihydro-1,2-azaborine involves both photoreactions and thermal reactions. The calculated results clarify recent experimental observations.

Conical intersection seam and bound resonances embedded in continuum observed in the photodissociation of thioanisole-d3.

Herein, the multi-dimensional nature of the conical intersection seam has been experimentally revealed in the photodissociation reaction of thioanisole-d3 (C6H5SCD3) excited on S1, giving C6H5S·(à or X̃]) +·CD3 products. The translational energy distribution of the nascent·CD3 fragment, reflecting the relative yields of the C6H5S·(Ã) and C6H5S·(X̃) products, was measured at each S1 vibronic band using the velocity map ion imaging technique. Direct access of the reactant flux to the conical intersection seam leads to the increase of the nonadiabatic transition probability resulting in sharp resonances in the X̃/ÃC6H5S·product branching ratio at several distinct S1 vibronic bands. The nature of the S1 vibronic bands associated with such dynamic resonances was clarified by the mass-analyzed threshold ionization spectroscopy. The bound state embedded in continuum generated by the conical intersection is observed as a distinct dynamic resonance, revealing the nature of the nuclear motion responsible for the nonadiabatic coupling of two potential energy surfaces at the conical intersection. The multi-dimensional facets of the conical intersection seam in terms of its detailed structure and dynamic role are discussed with the aid of theoretical calculations.

Review of Gas-Chromatographic Measurement Methodologies for Atmospheric Halogenated Greenhouse Gases.

Gas chromatography (GC) is crucial for measuring atmospheric halogenated greenhouse gases (hGHGs), usually coupled with electron capture detector (ECD, with higher sensitivity) or mass spectrometry (MS, with higher selectivity). This review compares GC-ECD and GC-MS for analyzing atmospheric hGHGs in terms of analytical methodology, performance, and instrumentation. For hGHGs such as SF6, chlorofluorocarbons, and N2O, ECD can be employed in the single column, forecut-backflush (FCBF), and preconcentration methods. The order of appearance of SF6 and N2O is an important consideration for selecting the separation column to avoid chromatographic interference from the long-tailed N2O and O2 on SF6. Single column and FCBF GC-ECD methods suffer from nonlinear responsivity, but the preconcentration method can compensate for nonlinearity. The last method also offers a low drift, which eliminates the need for multipoint calibration and enables perfect linearity at atmospheric SF6 levels. GC-MS demonstrates strong separability and identification capabilities, and over 60 hGHGs can be qualitatively analyzed by leveraging the separation power of MS and established MS databases. However, GC-MS requires a preconcentrator operating at -165 °C utilizing specialized adsorbents. Two notable preconcentrator-GC-MS systems, Medusa-GC-MS and detachable trap preconcentrator (DTP) GC-MS, differ in trap design, temperature scheme, and separation column type. Medusa-GC-MS employs a three-phased temperature operation before MS. DTP-GC-MS separates the preconcentration cycle into highly and less volatile compounds, using a different temperature scheme from that of Medusa-GC-MS. The preconcentrator-GC-MS system is widely employed for measuring perfluorocarbons, hydrofluorocarbons, and other hGHGs. This method necessitates multiple adsorption traps to discriminate the most abundant air components.

Isotope ratios of total C, N, and S in particulate matter simultaneously calibrated by mixed USGS and IAEA reference materials.

This study presents a method for calibrating the isotope ratios of the total carbon, nitrogen, and sulfur in particulate matter (PM) collected from the Seoul metro using an elemental analyzer-isotope ratio mass spectrometer (EA-IRMS). Mixtures of isotope reference materials (MRMs) from the U.S. Geological Survey (USGS) and International Atomic Energy Agency (IAEA) reference materials formed an input dataset for generalized least squares (GLS) regression to yield calibration lines. The analytical method proposed in this study enabled the measurement of stable isotope ratios of total carbon, nitrogen, and sulfur simultaneously. Results showed good linearity and repeatability for carbon and nitrogen isotopes, but poor results for sulfur isotopes due to peak broadening. Reference values with uncertainties for the isotope ratios of total carbon, nitrogen, and sulfur were determined for the collected PM, demonstrating twice as much uncertainty as that of the USGS and IAEA reference materials. Homogeneity was the biggest uncertainty source for the calibrated values.

Photodissociation dynamics of the thiophenoxy radical at 248, 193, and 157 nm.

The photodissociation dynamics of the thiophenoxy radical (C6H5S) have been investigated using fast beam coincidence translational spectroscopy. Thiophenoxy radicals were produced by photodetachment of the thiophenoxide anion followed by photodissociation at 248 nm (5.0 eV), 193 nm (6.4 eV), and 157 nm (7.9 eV). Experimental results indicate two major competing dissociation channels leading to SH + C6H4 (o-benzyne) and CS + C5H5 (cyclopentadienyl) with a minor contribution of S + C6H5 (phenyl). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Transition states and minima for each reaction pathway were calculated using density functional theory to facilitate experimental interpretation. The proposed dissociation mechanism involves internal conversion from the initially prepared electronic excited state to the ground electronic state followed by statistical dissociation. Calculations show that SH loss involves a single isomerization step followed by simple bond fission. For both SH and S loss, C-S bond cleavage proceeds without an exit barrier. By contrast, the CS loss pathway entails multiple transition states and minima as it undergoes five membered ring formation and presents a small barrier with respect to products. The calculated reaction pathway is consistent with the experimental translational energy distributions in which the CS loss channel has a broader distribution peaking farther away from zero than the corresponding distributions for SH loss.

Dual isotope ratio normalization of nitrous oxide by bacterial denitrification of USGS reference materials.

We measured the δ values of N2O using gas chromatography isotope ratio mass spectrometry with a preconcentrator (precon-GC-IRMS). The instrumental precision of the mass spectrometer was restricted to below the shot noise limit, which agreed with the theoretical and experimental results of 0.02‰ (δ15N) and 0.04‰ (δ18O), respectively. The precision of the measured δ values was significantly improved by the temperature regulation protocol of the LN2 preconcentrator, which was monitored by various temperature sensors placed along the U-trap. The reproducibility of the He-diluted N2O gas measurements resulted in 0.063‰ (δ15N) and 0.075‰ (δ18O) due to additional sources of uncertainty in the vials used for autosampling and in the general preconcentration process. Multipoint normalization of the dual δ values of the measured N2O samples was conducted using United States Geological Survey reference materials denitrified by Pseudomonas aureofaciens. Kaiser's ion correction method, based on International Atomic Energy Agency parameters, exhibited low bias for the atomic isotope ratio reduction of the nitrate reference material, for which the oxygen anomaly was considerably high. Dedicated corrections for net isotope fractionation and water exchange were important in improving uncertainties in the procedure for normalizing the oxygen isotope ratio. Blank measurements for correcting biases in isotope ratios caused by pre-dissolved nitrate and nitrite ions in the water solvent led to further improvements, i.e. beyond unevenly controlled net isotope fractionation, throughout the bacterial denitrification process. The uncertainty evaluation revealed that three-point normalization can significantly improve the normalization accuracy compared with two-point normalization. In addition, an alternative strategy was suggested for assigning δ18O using a CO2 lab tank, allowing its use as a reference material for N2O gas tanks.

Photodissociation dynamics of thiophenol-d1: the nature of excited electronic states along the S-D bond dissociation coordinate.

The S-D bond dissociation dynamics of thiophenol-d1 (C6H5SD) pumped at 266, 243, and 224 nm are examined using the velocity map ion imaging technique. At both 266 and 243 nm, distinct peaks associated with X and A states of the phenylthiyl radical (C6H5S*) are observed in the D+ image at high and low kinetic energy regions, respectively. The partitioning of the available energy into the vibrational energy of the phenylthiyl radical is found to be enhanced much more strongly at 266 nm compared to that at 243 nm. This indicates that the pipi* electronic excitation at 266 nm is accompanied by significant vibrational excitation. Given the relatively large anisotropy parameter of -0.6, the S-D dissociation at 266 nm is prompt and should involve the efficient coupling to the upper-lying n(pi)sigma* repulsive potential energy surface. The optical excitation of thiophenol at 224 nm is tentatively assigned to the pisigma* transition, which leads to the fast dissociation on the repulsive potential energy surface along the S-D coordinate. The nature of the electronic transitions associated with UV absorption bands is investigated with high-level ab initio calculations. Excitations to different electronic states of thiophenol result in unique branching ratios and vibrational excitations for the fragment of the phenylthiyl radical in the two lowest electronic states.

Multipoint normalization of δ18O of water against the VSMOW2-SLAP2 scale with an uncertainty assessment.

In this study, we measured the oxygen stable isotope ratio of drinking water using gas chromatography isotope ratio mass spectrometry. The δ18O value of drinking water was normalized based on the Vienna Standard Mean Ocean Water 2 (VSMOW2), Standard Light Antarctic Precipitation 2 (SLAP2), and Greenland Ice Sheet Precipitation (GISP) scale by CO2 equilibrium for 24 h. The isotope ratio responses of a dummy sample drifted as much as 0.145‰ due to a significant decrease in the amount of injected sample. The autodilution technique improved measurement precision of the δ18O of dummy sample two-fold compared to that without autodilution to 0.025‰. The autodilution of an injected concentration of equilibrated CO2 also helped improve the measurement precision of the isotope ratio response. The drift of the ratio responses was tested using linear model regression to validate linearity within the sample concentration and isotope ratio ranges. Measurement reliability was assessed using various statistical approaches. One-way analysis of variance verified non-reproducible results of individual measurements. Normalization uncertainties were then assessed by various normalization schemes including two-point and three-point values consisting of the VSMOW2, SLAP2, and GISP standards, showing equivalent results associated with similar extent of normalization uncertainties among various normalization methods. In particular, the uncertainty of the GISP (0.09‰) contributed to one-third of the total normalization uncertainty, implying that the three-point normalization can be improved by a potential standard of which uncertainty is equivalent to the bracketing standards, VSMOW2 (0.02‰) and SLAP2 (0.02‰).

Analysis of trace impurities in neon by a customized gas chromatography.

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-µmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378µmol/mol; O2, 0.119µmol/mol; CH4, 0.880µmol/mol; CO, 0.263µmol/mol; CO2, 0.162µmol/mol (PDNeD); and He, 0.190µmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne.

Experimental probing of conical intersection dynamics in the photodissociation of thioanisole.

Chemical reactions that occur in the ground electronic state are described well by invoking the Born-Oppenheimer approximation, which allows their development to be rationalized by nuclear rearrangements that smoothly traverse an adiabatic potential energy surface. The situation is different, however, for reactions in electronically excited states, where non-adiabatic transitions occur between adiabatic surfaces. The conical intersection, in which two adiabatic surfaces touch, is accepted widely as the dynamic funnel for efficient non-adiabatic transitions, but its direct experimental probing is rare. Here, we investigate the photodissociation of thioanisole and observe a striking dependence of the relative yields of two reaction channels on the photoexcitation energy as indicated by a dynamic resonance in the product branching ratio. This results from the interference of two different adiabatic states that are in close proximity in the region of a conical intersection. The location of the observed resonance on the multidimensional potential energy surface thus reveals the nuclear configuration of the conical intersection and its dynamic role in the non-adiabatic transition.

Experimental and theoretical study of the photodissociation reaction of thiophenol at 243 nm: intramolecular orbital alignment of the phenylthiyl radical.

The photoinduced hydrogen (or deuterium) detachment reaction of thiophenol (C(6)H(5)SH) or thiophenol-d(1) (C(6)H(5)SD) pumped at 243 nm has been investigated using the H (D) ion velocity map imaging technique. Photodissociation products, corresponding to the two distinct and anisotropic rings observed in the H (or D) ion images, are identified as the two lowest electronic states of phenylthiyl radical (C(6)H(5)S). Ab initio calculations show that the singly occupied molecular orbital of the phenylthiyl radical is localized on the sulfur atom and it is oriented either perpendicular or parallel to the molecular plane for the ground (B(1)) and the first excited state (B(2)) species, respectively. The experimental energy separation between these two states is 2600+/-200 cm(-1) in excellent agreement with the authors' theoretical prediction of 2674 cm(-1) at the CASPT2 level. The experimental anisotropy parameter (beta) of -1.0+/-0.05 at the large translational energy of D from the C(6)H(5)SD dissociation indicates that the transition dipole moment associated with this optical transition at 243 nm is perpendicular to the dissociating S-D bond, which in turn suggests an ultrafast D+C(6)H(5)S(B(1)) dissociation channel on a repulsive potential energy surface. The reduced anisotropy parameter of -0.76+/-0.04 observed at the smaller translational energy of D suggests that the D+C(6)H(5)S(B(2)) channel may proceed on adiabatic reaction paths resulting from the coupling of the initially excited state to other low-lying electronic states encountered along the reaction coordinate. Detailed high level ab initio calculations adopting multireference wave functions reveal that the C(6)H(5)S(B(1)) channel may be directly accessed via a (1)(n(pi),sigma(*)) photoexcitation at 243 nm while the key feature of the photodissociation dynamics of the C(6)H(5)S(B(2)) channel is the involvement of the (3)(n(pi),pi(*))-->(3)(n(sigma),sigma(*)) profile as well as the spin-orbit induced avoided crossing between the ground and the (3)(n(pi),sigma(*)) state. The S-D bond dissociation energy of thiophenol-d(1) is accurately estimated to be D(0)=79.6+/-0.3 kcalmol. The S-H bond dissociation energy is also estimated to give D(0)=76.8+/-0.3 kcalmol, which is smaller than previously reported ones by at least 2 kcalmol. The C-H bond of the benzene moiety is found to give rise to the H fragment. Ring opening reactions induced by the pi-pi(*)n(pi)-pi(*) transitions followed by internal conversion may be responsible for the isotropic broad translational energy distribution of fragments.