IUPAC Task Group Research Articles

Living and controlled reversible‐activation polymerization (RAP) on the way to reversible‐deactivation radical polymerization (RDRP)

AbstractIn 2010, an IUPAC task group comprising Aubrey Jenkins, Dick Jones and Graeme Moad coined ‘reversible‐deactivation radical polymerization (RDRP)’ as a new term to describe what up to that time had been known variously as living or controlled radical polymerization. This paper describes the steps and missteps in the terminological development of RDRP. The paper that introduced the term is currently one of the more highly cited IUPAC terminology papers. © 2022 Commonwealth of Australia. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Impact of pyruvic acid photolysis on acetaldehyde and peroxy radical formation in the boreal forest: theoretical calculations and model results

Abstract. Based on the first measurements of gas-phase pyruvic acid (CH3C(O)C(O)OH) in the boreal forest, we derive effective emission rates of pyruvic acid and compare them with monoterpene emission rates over the diel cycle. Using a data-constrained box model, we determine the impact of pyruvic acid photolysis on the formation of acetaldehyde (CH3CHO) and the peroxy radicals CH3C(O)O2 and HO2 during an autumn campaign in the boreal forest. The results are dependent on the quantum yield (φ) and mechanism of the photodissociation of pyruvic acid and the fate of a likely major product, methylhydroxy carbene (CH3COH). With the box model, we investigate two different scenarios in which we follow the present IUPAC (IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation, 2021) recommendations with φ = 0.2 (at 1 bar of air), and the main photolysis products (60 %) are acetaldehyde + CO2 with 35 % C–C bond fission to form HOCO and CH3CO (scenario A). In the second scenario (B), the formation of vibrationally hot CH3COH (and CO2) represents the main dissociation pathway at longer wavelengths (∼ 75 %) with a ∼ 25 % contribution from C–C bond fission to form HOCO and CH3CO (at shorter wavelengths). In scenario 2 we vary φ between 0.2 and 1 and, based on the results of our theoretical calculations, allow the thermalized CH3COH to react with O2 (forming peroxy radicals) and to undergo acid-catalysed isomerization to CH3CHO. When constraining the pyruvic acid to measured mixing ratios and independent of the model scenario, we find that the photolysis of pyruvic acid is the dominant source of CH3CHO with a contribution between ∼ 70 % and 90 % to the total production rate. We find that the photolysis of pyruvic acid is also a major source of the acetylperoxy radical, with contributions varying between ∼ 20 % and 60 % dependent on the choice of φ and the products formed. HO2 production rates are also enhanced, mainly via the formation of CH3O2. The elevated production rates of CH3C(O)O2 and HO2 and concentration of CH3CHO result in significant increases in the modelled mixing ratios of CH3C(O)OOH, CH3OOH, HCHO, and H2O2.

Evaluated kinetic and photochemical data for atmospheric chemistry: volume VIII – gas-phase reactions of organic species with four, or more, carbon atoms ( ≥ C4)

Abstract. This article, the eighth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the gas-phase thermal and photochemical reactions of organic species with four, or more, carbon atoms (≥ C4) available on the IUPAC website in 2021, including thermal reactions of closed-shell organic species with HO and NO3 radicals and their photolysis. The present work is a continuation of volume II (Atkinson et al., 2006), with new reactions and updated data sheets for reactions of HO (77 reactions) and NO3 (36 reactions) with ≥ C4 organics, including alkanes, alkenes, dienes, aromatics, oxygenated, organic nitrates and nitro compounds in addition to photochemical processes for nine species. The article consists of a summary table (Table 1), containing the recommended kinetic parameters for the evaluated reactions, and a supplement containing the data sheets, which provide information upon which recommendations are made.

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates

Abstract. This article, the seventh in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers an extension of the gas-phase and photochemical reactions related to Criegee intermediates previously published in Atmospheric Chemistry and Physics (ACP) in 2006 and implemented on the IUPAC website up to 2020. The article consists of an introduction, description of laboratory measurements, a discussion of rate coefficients for reactions of O3 with alkenes producing Criegee intermediates, rate coefficients of unimolecular and bimolecular reactions and photochemical data for reactions of Criegee intermediates, and an overview of the atmospheric chemistry of Criegee intermediates. Summary tables of the recommended kinetic and mechanistic parameters for the evaluated reactions are provided. Data sheets summarizing information upon which the recommendations are based are given in two files, provided as a Supplement to this article.

The far-infrared spectrum of 18O enriched water vapour (40–700 cm−1)

The rotational spectrum of water vapour highly enriched in 18O has been studied by high resolution (≈ 0.001 cm−1) Fourier transform spectroscopy at the AILES beam line of the SOLEIL synchrotron. The room temperature absorption spectrum has been recorded between 40 and 700 cm−1. The 18O enrichment of the sample was about 97% while the gas pressure and the absorption pathlength were set to 0.97 mbar and 151.75 m, respectively. The spectrum contains more than 4800 rotational transitions from seven water isotopologues (H218O, H216O, H217O, HD18O, HD16O, HD17O, D218O). The assignments were performed using known experimental energy levels as well as calculated line lists based on the results of Schwenke and Partridge. The amount and accuracy of the reported line positions represent an important extension compared to previous works. Overall, lines of about 2570 transitions are observed for the first time and 35, 41, 50, and 16 new energy levels are determined for H218O, H217O, HD18O, and HD17O, respectively. The set of derived energy levels shows a number of important differences from those recommended by an IUPAC-task group. Compared to the HITRAN2016 database, numerous deviations of line positions (up to 0.15 cm−1) are found for the H217O, H218O, HD17O, and HD18O species. Incomplete and wrong HITRAN's assignments of more than 90 transitions for H218O, H217O and HD18O are identified. Overall, the measured line positions will allow to significantly refine and complete the sets of empirical energy levels of H218O, H217O, HD18O and HD17O in the ground vibrational state.

New transitions and energy levels of water vapor by high sensitivity CRDS near 1.73 and 1.54 µm

This contribution is part of a long term project aiming at improving the water absorption spectroscopy by high sensitivity cavity ring down spectroscopy (CRDS) in the near infrared.Two new sources of CRDS spectra are considered:(i) The room temperature absorption spectrum of water vapor in natural isotopic abundance is recorded near 1.73 µm. A series of recordings was performed from 5693 to 5991 cm−1 with a pressure value of about 6 Torr. The noise equivalent absorption (αmin) of the spectra is better than 10−10 cm−1. A total of 1453 lines were assigned to 1573 transitions of four water isotopologues (H216O, H217O, H218O and HD16O). Their intensities span more than five orders of magnitude from 3.0 × 10−30 to 4.7 × 10−25 cm/molecule at 296 K. The assignments were performed using known experimental energy levels as well as calculated line lists based on the results of Schwenke and Partridge.Two hundred fifty-one lines (assigned to 280 transitions) are observed for the first time and twelve energy levels are newly determined. The comparison of the obtained line parameters with those of the HITRAN database is discussed. Forty-six line positions are observed to significantly differ from their HITRAN values (δν = │νHITRAN – νCRDS│ > 0.02 cm−1). The derived set of energy levels is compared to those recommended by an IUPAC task group.(ii) The room temperature CRDS spectrum of water vapor highly enriched in 17O was recorded near 1.54 µm (6223–6672 cm−1) at a pressure of 12 Torr. Compared to a previous study, the higher pressure of the recordings allowed for extending the observations. Overall, twenty-six new levels were determined for both H217O and HD17O.All these observations together with other recent measurements will allow for an extension and an update of our empirical database in the 5693– 8340 cm−1 region.

Cavity ring down spectroscopy of 17O enriched water vapor near 1.73 µm

The room temperature absorption spectrum of water vapour highly enriched in 17O is recorded by cavity ring down spectroscopy (CRDS) near 1.73 µm. Two series of recordings were performed with pressure values of about 0.12 and 8.5 Torr from 5693 to 5850 cm−1. The noise equivalent absorption (αmin) of the spectra is better than 10−10 cm−1 allowing for the measurements of water lines with intensity down to 10−29 cm/molecule. A total of 1132 lines were assigned to 1220 transitions of five water isotopologues (H216O, H217O, H218O, HD16O, and HD17O). Their intensities span near five orders of magnitude from 10−29 to 10−24 cm/molecule at 296 K. The assignments were performed using known experimental energy levels as well as calculated line lists based on the results of Schwenke and Partridge.Most of the new results concern the H217O isotopologue: 483 transitions were measured while only the 27 strongest were previously known. Overall 104 levels were newly determined for H217O (64 levels), H218O (16), HD17O (23) and HD16O (1) and a few additional levels were corrected compared to the literature. The obtained results are compared to the water line list in the HITRAN2016 database, to the ExoMol energy levels and to the empirical energy levels recommended by an IUPAC task group.

IUPAC in the (real) clouds

Abstract As we approach the end of the second decade of the 21st century, changes in atmospheric chemical composition due to anthropogenic pollution continue to challenge the well-being of society. The IUPAC effort in atmospheric chemistry data evaluation can be traced back over 40 years. Global concerns over potentially catastrophic stratospheric ozone depletion resulting from emissions of chlorofluorocarbons (CFCs) led to the creation of the CODATA Task Group on Chemical Kinetics in 1977. The task of the CODATA group was to provide the evaluated kinetic data for atmospheric reactions needed to assess the threat to stratospheric ozone. In 1989, sponsorship of the data evaluation effort was transferred to IUPAC, leading to the formation of the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation.

CRDS of 17O enriched water between 5850 and 6671 cm−1: More than 1000 energy levels of H217O and HD17O newly determined

The room temperature absorption spectrum of water vapor highly enriched in 17O has been recorded by Cavity Ring Down Spectroscopy (CRDS) between 5850 and 6671cm−1. Two series of recordings were performed with pressure values of 1.0 and 12.0Torr. The investigated spectral region corresponds to the important 1.55μm transparency window of the atmosphere where water absorption is very weak. The high sensitivity of the recordings (αmin ~ 5×10−11cm−1) allows detecting lines with intensity spanning six orders of magnitude (1.4×10−30–3.6×10−24cm/molecule at room temperature). The experimental list includes more than 10,300 lines. The assignments of water lines were performed using known experimental energy levels as well as calculated line lists based on the results of Partridge and Schwenke. More than 8500 lines were assigned to 9619 transitions of six water isotopologues (H216O, H217O, H218O, HD16O, HD17O and HD18O). All but four transitions of the 16O and 18O isotopologues were assigned using known experimental energy levels. More than half of the assigned H217O and HD17O transitions correspond to new (or corrected) upper energy levels. About 1000 new H217O transitions associated with upper states of the second triad and of the first hexad were identified. Most of the newly assigned HD17O transitions belong to the ν1+ν3 and 2ν2+ν3 bands. The assigned transitions allowed to newly determine or correct 20 highly excited rotational levels of the vibrational ground state of this isotopologue. Overall 791 and 266 energy levels are newly determined for H217O and HD17O, respectively. A few additional levels were corrected compared to literature values. The obtained experimental results are compared to the spectroscopic parameters provided by the HITRAN database and to the empirical energy levels recommended by an IUPAC task group.

The absorption spectrum of water vapor in the 1.25 μm atmospheric window (7911–8337 cm−1)

The absorption spectrum of water vapor in “natural” isotopic abundance has been recorded at room temperature by high sensitivity Continuous Wave Cavity Ring Down Spectroscopy (CW-CRDS) between 7911 and 8337cm−1. The investigated region covers most of the 1.25µm transparency window of importance for atmospheric applications. The recordings were performed with sensitivity on the order of αmin~2×10–11cm−1, more than two orders of magnitude better than previous investigations by Fourier Transform Spectroscopy (FTS). Measured line intensities cover a range of seven orders of magnitude (3×10–30–2×10–23cm/molecule at room temperature). The experimental line list provided as Supplementary Material includes more than 5000 transitions. As a result of the achieved sensitivity, more than 1150 lines of the experimental list were identified as being due to ammonia present as an impurity at the 5ppm concentration level in the water sample. Although incomplete, the obtained ammonia line list seems to be the first one in the region. More than 3193 water lines were assigned to 3560 transitions of five water isotopologues (H216O, H218O, H217O, HD16O and HD18O). The assignments were performed using known experimental energy levels and calculated spectra based on variational calculations by Schwenke and Partridge. The obtained results are compared to the most relevant previous studies by Fourier Transform Spectroscopy in the region and to the exhaustive review of rovibrational line positions and levels performed recently by an IUPAC sponsored task group. Two-hundred and sixty-six levels are newly determined and 46 are corrected by more than 0.015cm−1 compared to those recommended by the water IUPAC task group. The overall agreement between variational and measured intensities is satisfactory.A complete empirical list of 4473 transitions incorporating all the experimental information at disposal was constructed for water in the studied region. The intensity cut-off was fixed to 1×10–29cm/molecule at 296K. A detailed comparison with the line list as provided by the HITRAN database illustrates the advantages of the new list.

Recommended isolated-line profile for representing high-resolution spectroscopic transitions (IUPAC Technical Report)

Abstract The report of an IUPAC Task Group, formed in 2011 on “Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory” (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile (pCqSD-HCP) should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann–Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.

CW-Cavity Ring Down Spectroscopy of deuterated water in the 1.58 μm atmospheric transparency window

The spectrum of water vapour enriched in deuterium has been recorded by highly sensitive CW-Cavity Ring Down Spectroscopy in the 5855–6802cm−1 spectral region. The studied region includes the 1.58µm atmospheric transparency window of particular interest for remote sensing. More than 8000 absorption lines belonging to eight water isotopologues – H216O, H218O HD16O, D216O, HD18O, D218O, HD17O and D217O – were identified.The spectrum was assigned using both the IUPAC database of experimental transitions and energy levels, and accurate variational calculations. Overall, 1396 and 1277 experimental energy levels belonging to 18 and 16 upper vibrational states were retrieved for the HD16O and D216O species, respectively. 773 energy levels are newly derived. New experimental information concerns the high J (up to 20) and high Ka (up to 12) energy levels of the (101), (021), (040), (210), (120) states of HD16O and of the (111), (031), (210), (012), (130) states of D216O. While only a few energy levels were available, the rotational structure of the (130) and (220) states of HD16O could be analysed in detail. Rotational sublevels of the (140) state of D216O are reported for the first time. A detailed comparison of the derived energy levels with the values recommended by an IUPAC task group is presented. In particular, a significant improvement is evidenced for a number of quasi degenerate energy levels of HD16O. The obtained results are also discussed in relation with several recent studies.

A database of water transitions from experiment and theory (IUPAC Technical Report)

Abstract The report and results of an IUPAC Task Group (TG) formed in 2004 on “A Database of Water Transitions from Experiment and Theory” (Project No. 2004-035-1-100) are presented. Energy levels and recommended labels involving exact and approximate quantum numbers for the main isotopologues of water in the gas phase, H2 16O, H2 18O, H2 17O, HD16O, HD18O, HD17O, D2 16O, D2 18O, and D2 17O, are determined from measured transition frequencies. The transition frequencies and energy levels are validated using first-principles nuclear motion computations and the MARVEL (measured active rotational–vibrational energy levels) approach. The extensive data including lines and levels are required for analysis and synthesis of spectra, thermochemical applications, the construction of theoretical models, and the removal of spectral contamination by ubiquitous water lines. These datasets can also be used to assess where measurements are lacking for each isotopologue and to provide accurate frequencies for many yet-to-be measured transitions. The lack of high-quality frequency calibration standards in the near infrared is identified as an issue that has hindered the determination of high-accuracy energy levels at higher frequencies. The generation of spectra using the MARVEL energy levels combined with transition intensities computed using high accuracy ab initio dipole moment surfaces are discussed. A recommendation of the TG is for further work to identify a single, suitable model to represent pressure- (and temperature-) dependent line profiles more accurately than Voigt profiles.

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates

Abstract. This article, the sixth in the ACP journal series, presents data evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the heterogeneous processes involving liquid particles present in the atmosphere with an emphasis on those relevant for the upper troposphere/lower stratosphere and the marine boundary layer, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website since 2009. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. The experimental data on which the recommendations are based are provided in data sheets in separate appendices for the four surfaces considered: liquid water, deliquesced halide salts, other aqueous electrolytes and sulfuric acid.

An improved line list for water vapor in the 1.5 µm transparency window by highly sensitive CRDS between 5852 and 6607 cm−1

The absorption spectrum of water vapor in “natural” isotopic abundance has been recorded by high sensitivity Continuous Wave Cavity Ring Down Spectroscopy (CW-CRDS) between 5852 and 6607cm−1. The investigated region covers the 1.5µm transparency window of major importance for atmospheric applications. The achieved sensitivity of the recordings varies from αmin ∼2×10−11 to 2×10−10cm−1 and allows for a significant amount of new or more accurate observations compared to previous studies. Measured line intensities cover a range of six orders of magnitude (2×10−30−2×10−24cm/molecule at room temperature). The vibration–rotation assignments were performed using known experimental energy levels and calculated spectra based on variational calculations by Schwenke and Partridge.Five thousand seven hundred and twenty seven lines were assigned to 6379 transitions of six water isotopologues (H216O, H218O, H217O, HD16O, HD18O and HD17O). The first detection of lines due to HD17O in “natural” water (relative abundance on the order of 1.1×10−7) illustrates the sensitivity of the recordings. Most of the 1842 newly reported transitions belong to the main isotopologue (1022 transitions) and to the HD16O isotopologue (684 transitions). Sixty-three levels are newly determined and 22 are corrected by more than 0.015cm−1 compared to those recommended by the water IUPAC task group.Overall, a list of 6589 transitions was constructed for the studied region. The present CRDS line list complemented with 210 strong transitions from the literature is believed to be the most complete empirical list of the region. The obtained results are critically compared to recent IUPAC task group compilations. Overall the agreement between variational and measured intensities is very satisfactory. We nevertheless point out a number of important disagreements for some lines of the highly excited bending bands, mainly 4ν2 of H216O.

Quality assessment of NMR structures: a statistical survey

A statistical analysis is reported of experimental data and coordinates of a set of 97 NMR structures deposited in the PDB. The aim is to assess the quality of these structures in relation to the amount of experimental information. Experimental restraints were analysed using the program AQUA. Many nomenclature inconsistencies between deposited restraint and coordinate files were observed. The experimental restraint files were found to contain a high proportion of redundant restraints. Procedures for analysing and correcting the inconsistencies and restraint counts are described. The analysis of NOE restraint violations (using AQUA) and of a wide variety of geometrical quality indicators (using PROCHECK-NMR and WHAT IF) provides a reference for other NMR structure determinations. The extent of NOE violations is anti-correlated with the quality of the Ramachandran map. The precision as measured by the circular variance of backbone dihedral angles, does increase with the amount of experimental data, as expected, but is sometimes overestimated. Bond lengths, bond angles and planarity of groups can deviate considerably from ideal values. Outliers appear to cluster per laboratory, indicating that the results depend on particulars of refinement protocols and/or software. We have identified a problem of atom overlap in a number of refined structures. We recommend adhering to the standard nomenclature as put forward by an IUPAC Task Group, to ensure consistency between restraints and coordinates, and to omit redundant restraints from the deposition. The results obtained from this analysis and the AQUA program are available through the World Wide Web.

The nonadiabatic reaction between carbon monoxide and atomic oxygen

The room temperature absorption spectrum of water vapor highly enriched in 17O has been recorded by Cavity Ring Down Spectroscopy (CRDS) between 5850 and 6671 cm−1. Two series of recordings were performed with pressure values of 1.0 and 12.0 Torr. The investigated spectral region corresponds to the important 1.55 μm transparency window of the atmosphere where water absorption is very weak. The high sensitivity of the recordings (αmin ~ 5×10−11 cm−1) allows detecting lines with intensity spanning six orders of magnitude (1.4×10−30–3.6×10−24 cm/molecule at room temperature). The experimental list includes more than 10,300 lines. The assignments of water lines were performed using known experimental energy levels as well as calculated line lists based on the results of Partridge and Schwenke. More than 8500 lines were assigned to 9619 transitions of six water isotopologues (H216O, H217O, H218O, HD16O, HD17O and HD18O). All but four transitions of the 16O and 18O isotopologues were assigned using known experimental energy levels. More than half of the assigned H217O and HD17O transitions correspond to new (or corrected) upper energy levels. About 1000 new H217O transitions associated with upper states of the second triad and of the first hexad were identified. Most of the newly assigned HD17O transitions belong to the ν1+ν3 and 2ν2+ν3 bands. The assigned transitions allowed to newly determine or correct 20 highly excited rotational levels of the vibrational ground state of this isotopologue. Overall 791 and 266 energy levels are newly determined for H217O and HD17O, respectively. A few additional levels were corrected compared to literature values. The obtained experimental results are compared to the spectroscopic parameters provided by the HITRAN database and to the empirical energy levels recommended by an IUPAC task group.