The last 12 months have provided further evidence of the potential for cascading ecological and socio-political crises that were warned of 12 months ago. Then a consensus statement from the Regional Action on Climate Change Symposium warned: “the Earth’s climatic, ecological, and human systems are converging towards a crisis that threatens to engulf global civilization within the lifetimes of children now living.” Since then, the consequences of a broad set of extreme climate events (notably droughts, floods, and fires) have been compounded by interaction with impacts from multiple pandemics (including COVID-19 and cholera) and the Russia–Ukraine war. As a result, new connections are becoming visible between climate change and human health, large vulnerable populations are experiencing food crises, climate refugees are on the move, and the risks of water, food, and climate disruption have been visibly converging and compounding. Many vulnerable populations now face serious challenges to adapt. In light of these trends, this year, RACC identifies a range of measures to be taken at global and regional levels to bolster the resilience of these populations in the face of such emerging crises. In particular, at all scales, there is a need for globally available local data, reliable analytic techniques, community capacity to plan adaptation strategies, and the resources (scientific, technical, cultural, and economic) to implement them. To date, the rate of growth of the support for climate change resilience lags behind the rapid growth of cascading and converging risks. As an urgent message to COP27, it is proposed that the time is now right to devote much greater emphasis, global funding, and support to the increasing adaptation needs of vulnerable populations.

Two separate temperature-dependent experiments were performed to investigate the ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) of matrix 2,5-dihydroxybenzoic acid (2,5-DHB). First, the angular resolved intensity and velocity distributions of neutrals desorbed from the 2,5-DHB solid sample through UV laser (355 nm) pulse irradiation were measured using a rotating quadrupole mass spectrometer. Second, the desorbed neutrals, at an angle normal to the surface, and the desorbed ions were simultaneously detected for each laser shot using the quadrupole mass spectrometer and a time-of-flight mass spectrometer, respectively. Both experiments were conducted at two initial temperatures: 100 and 300 K. The measurements from these two experiments were used to calculate the initial temperature dependence of the ion-to-neutral ratio. The results closely agreed with the predictions of the temperature-dependent ion-to-neutral ratio using the thermal model, indicating that thermally induced proton transfer is the dominant reaction that generates initial ions of 2,5-DHB in UV-MALDI.

The reaction of Criegee intermediate CH2OO with HCOOH is important in atmospheric chemistry, but its mechanism and kinetics are little investigated. We recorded time-resolved infrared absorption spectra of transient species produced upon irradiation at 308 nm of a flowing mixture of CH2I2/O2/N2/HCOOH at 298 K. Bands of CH2OO were observed initially upon irradiation; their decrease was accompanied with the appearance of several bands near 887, 925, 1052, 1115, 1170, 1342, 1391, and 1760 cm-1, assigned to the absorption of hydroperoxymethyl formate [HC(O)OCH2OOH, HPMF], that decreased in intensity at a later period with the appearance of absorption bands of the anti-conformer of formic acid anhydride [anti-(HCO)2O, FAN] near 998, 1101, 1767, and 1821 cm-1. The main contributions of the infrared absorption of HPMF are from an open-form conformer, but small contributions from the intramolecular hydrogen-bonded conformer that absorbs near 1070, 1170, and 1732 cm-1 were identified. Observed infrared spectra of both conformers of HPMF and anti-FAN agree satisfactorily with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3LYP/aug-cc-pVTZ method. We derived a rate coefficient for CH2OO + HCOOH to be k = (1.4 ± 0.3) × 10-10 cm3 molecule-1 s-1 from formation of HPMF. We found also that anti-FAN was produced mainly from the open-form conformer with rate coefficient k = (1460 ± 30) s-1; the intramolecular hydrogen-bonded conformer of HPMF is stable.

We recorded time-resolved infrared absorption spectra of transient species produced on irradiation at 308 nm of a flowing mixture of CH2I2/O2/N2/SO2 at 298 K. Bands of CH2OO were observed initially upon irradiation; their decrease in intensity was accompanied by the appearance of an intense band at 1391.5 cm-1 that is associated with the degenerate SO-stretching mode of SO3, two major bands of HCHO at 1502 and 1745 cm-1, and five new bands near >1340, 1225, 1100, 940, and 880 cm-1. The band near 1340 cm-1 was interfered by absorption of SO2 and SO3, so its band maximum might be greater than 1340 cm-1. SO3 in its internally excited states was produced initially and became thermalized at a later period. The rotational contour of the band of thermalized SO3 agrees satisfactorily with the reported spectrum of SO3. These five new bands are tentatively assigned to an intermediate 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] according to comparison with anharmonic vibrational wavenumbers and relative IR intensities predicted for this intermediate. Observation of a small amount of cyc-(CH2)O(SO2)O is consistent with the expected reaction according to the potential energy scheme predicted previously. SO3+HCHO are the major products of the title reaction. The other predicted product channel HCOOH+SO2 was unobserved and its branching ratio was estimated to be <5%.

Polycyclic aromatic hydrocarbons (PAH) and their derivatives are prospective carriers of unidentified infrared (UIR) emission features observed in interstellar media. Fluoranthene (C16H10) is a simple planar PAH with five- and six-membered rings; it can be considered as a fragment of C60, which, along with its cationic counterpart, has been identified in interstellar media. Protonated fluoranthene, C16H11+, was generated upon electron bombardment during deposition at 3.2 K of p-H2 containing fluoranthene in a small proportion. The intensities of infrared features of C16H11+ decreased after maintaining the matrix in darkness because of its neutralization with trapped electrons. According to the correlations in intensities upon neutralization and secondary photolysis, observed lines were classified into three groups which are assigned to isomers 3-C16H11+, 9-C16H11+, and 10-C16H11+. Experimental vibrational wavenumbers and relative IR intensities of the features agree with corresponding calculated values predicted for these three isomers of C16H11+ with the B3PW91/6-311++G(2d,2p) method. 3-C16H11+ and 9-C16H11+ are predicted to have the lowest energy (within 5 kJ mol-1), whereas 10- and 1-C16H11+ are lying above the global minimum 3-C16H11+ by ∼20 kJ mol-1. However, definitive identification of 1-C16H11+ could not be made as only the most intense line is tentatively assigned. Although the observed spectra of these isomers match unsatisfactorily with the UIR bands, they will facilitate the potential terrestrial and extraterrestrial identification of these species.

The Criegee intermediates, carbonyl oxides produced in ozonolysis of unsaturated hydrocarbons, play important roles in atmospheric chemistry. The two conformers of CH3CHOO exhibit distinct reactivity toward several atmospheric species, but a distinct conformer-specific probe is challenging because ultraviolet and infrared absorption bands of syn- and anti-CH3CHOO overlap at low-resolution. Employing a quantum-cascade laser and a Herriott cell, we recorded the O-O stretching bands of CH2OO and syn-CH3CHOO in region 880-932 cm-1 at resolution 0.0015 cm-1. In addition to completely resolved vibration-rotational lines of CH2OO extending over 50 cm-1, some spectral lines associated with hot bands were identified. Spectral lines solely due to syn-CH3CHOO were also identified. Probing these lines, we determined the rate coefficient for the self-reaction of syn-CH3CHOO to be kself = (1.6 ± 0.60.5) × 10-10 cm3 molecule-1 s-1, about twice that of CH2OO.

Phenol is an important model molecule for the theoretical and experimental investigation of dissociation in the multistate potential energy surfaces. Recent theoretical calculations [X. Xu et al., J. Am. Chem. Soc. 136, 16378 (2014)] suggest that the phenoxyl radical produced in both the X and A states from the O-H bond fission in phenol can contribute substantially to the slow component of photofragment translational energy distribution. However, current experimental techniques struggle to separate the contributions from different dissociation pathways. A new type of time-resolved pump-probe experiment is described that enables the selection of the products generated from a specific time window after molecules are excited by a pump laser pulse and can quantitatively characterize the translational energy distribution and branching ratio of each dissociation pathway. This method modifies conventional photofragment translational spectroscopy by reducing the acceptance angles of the detection region and changing the interaction region of the pump laser beam and the molecular beam along the molecular beam axis. The translational energy distributions and branching ratios of the phenoxyl radicals produced in the X, A, and B states from the photodissociation of phenol at 213 and 193 nm are reported. Unlike other techniques, this method has no interference from the undissociated hot molecules. It can ultimately become a standard pump-probe technique for the study of large molecule photodissociation in multistates.

The reaction of hydrogen atoms (H) with isoprene (C5H8) in solid para-hydrogen (p-H2) matrices at 3.2 K has been studied using infrared (IR) spectroscopy. Mixtures of C5H8 and Cl2 were co-deposited in p-H2 at 3.2 K, followed by irradiation with ultraviolet light at 365 nm to produce Cl atoms from the Cl2, and subsequent irradiation with IR light to produce H atoms from the reaction of the Cl atoms with p-H2. The H atoms then react with the C5H8 to form H atom addition radicals (C5H9•). Upon 365-nm/IR photolysis, a multitude of new lines appeared in the IR spectrum and, based on the secondary photolysis behavior, it was determined that the majority of the new lines belong to two distinct chemical species, denoted as set X (an intense line at 776.0 cm-1 and 12 other weaker lines) and set Y (an intense line at 766.7 cm-1 and 12 other weaker lines). Quantum-chemical calculations were performed at the B3PW91/6-311++G(2d,2p) level to determine the relative energetics and predict the IR spectra for the four possible isomers of C5H9• that can be produced from the addition of the H atom to the four distinct carbon atoms in C5H8. The newly observed lines of set X and Y are assigned to the 1,2-dimethylallyl (addition to carbon 4) and the 1,1-dimethylallyl (addition to carbon 1) radicals according to comparison with the predicted IR spectra of the possible products. The 1,2-dimethylallyl radical and the 1,1-dimethylallyl radical were predicted to be the most stable isomers, with the latter ∼8 kJ mol-1 lower in energy than the former and to have significantly lower barriers than the addition pathways for the two central carbons. The ratio of the 1,1-dimethylallyl to the 1,2-dimethylallyl radicals is estimated to be (1.0 ± 0.5):1.0, indicating that the two radicals are produced in similar amounts, which is consistent with the theoretical predictions that the barrier heights are very similar for the H atom addition to the two terminal carbon atoms.

We report infrared (IR) spectra of HSCS+, c-HSCS, HCS2-, and other species produced on electron bombardment of a mixture of CS2 and para-hydrogen (p-H2) during deposition at 3.2 K. After maintenance of the deposited matrix in darkness for 12 h, the intensities of the absorption lines of HSCS+ at 2477.2 (ν1), 1525.6 (ν2), and 919.6 cm-1 (ν3) decreased through neutralization of HSCS+ with trapped electrons. During this period, the intensities of the lines of HCS2- at 2875.7 (ν1), 1249.9 (ν5), 1003.2 (ν6), and 814.3 cm-1 (ν4) increased due to reaction between H and CS2-. The intensities of the lines observed at 2312.7 and 889.0 cm-1, which are assigned to the c-HSCS radical, increased after maintenance in darkness and greatly diminished after irradiation at 373 nm. The IR spectra of HSCS+, HCS2-, and c-HSCS are reported for the first time. The IR absorption lines of the t-HSCS radical, t-HC(S)SH, and c-HC(S)SH were also identified; their wavenumbers are similar to those reported for these species in an Ar matrix. The corresponding spectra of the 13C, 34S, and D isotopic variants of these species were observed. The assignments were made according to the expected chemical behavior, predicted potential energies of associated reactions, and a comparison of observed and predicted wavenumbers and their 13C, 34S, and D isotopic ratios. In contrast to the observed significant red shifts of the OH-stretching wavenumbers of HOCO+ and HOCS+ in solid p-H2 compared to those in the gaseous phase due to proton sharing with H2, the wavenumber of the HS-stretching mode of HSCS+ in solid p-H2 (2477.2 cm-1) is similar to the anharmonic wavenumber of HSCS+ (2424 cm-1) predicted with the B3LYP/aug-cc-pVTZ method, indicating that the sharing of a proton between HSCS+ and neighboring H2 molecules is insignificant.

Yuan Tseh Lee was instrumental in the development and construction of an apparatus that utilized crossed molecular beams, presenting a break-through technique that allowed for the understanding of the dynamics of elementary chemical reactions. This was done by following the trajectories of reactants and reaction products in single collision events, allowing the visualization of the dynamics of how chemical reactions take place. This article also highlights Prof. Lee’s belief in the severity of the consequences of global warming and his concerns relating to the need to substantially reduce carbon emissions.

The kinetics and mechanisms for the reaction of the Criegee intermediate CH2OO with HNO3 and the unimolecular decomposition of its reaction product CH2(O)NO3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO3CH2OOH* with internal energy ∼44 kcal mol-1. A fragmentation of this excited intermediate produces CH2(O)NO3 + OH with its transition state located 5.0 kcal mol-1 below that of the reactants. Further decomposition of CH2(O)NO3 produces HCO + HNO3, forming a catalytic cycle for destruction of CH2OO by HNO3. The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N2) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH2OO + HNO3 at 295 K, 5.1 × 10-10 cm3 molecule-1 s-1, agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10-10 cm3 molecule-1 s-1. The predicted branching ratios at 295 K are 0.21 for the formation of NO3CH2OOH and 0.79 for CH2(O)NO3 + OH at a pressure of 40 Torr (N2), and 0.79 for the formation of NO3CH2OOH and 0.21 for CH2(O)NO3 + OH at 760 Torr (N2). This new catalytic conversion of CH2OO to HCO + OH by HNO3 might have significant impact on atmospheric chemistry.

The original ion imaging technique has low velocity resolution, and currently, photodissociation is mostly investigated using velocity map ion imaging. However, separating signals from the background (resulting from undissociated excited parent molecules) is difficult when velocity map ion imaging is used for the photodissociation of large molecules (number of atoms ≥ 10). In this study, we used the photodissociation of phenol at the S1 band origin as an example to demonstrate how our multimass ion imaging technique, based on modified spatial map ion imaging, can overcome this difficulty. The photofragment translational energy distribution obtained when multimass ion imaging was used differed considerably from that obtained when velocity map ion imaging and Rydberg atom tagging were used. We used conventional translational spectroscopy as a second method to further confirm the experimental results, and we conclude that data should be interpreted carefully when velocity map ion imaging or Rydberg atom tagging is used in the photodissociation of large molecules. Finally, we propose a modified velocity map ion imaging technique without the disadvantages of the current velocity map ion imaging technique.

The reaction of chlorine atoms (Cl) with isoprene (2-methyl-1,3-butadiene, C5H8) in solid para-hydrogen (p-H2) matrices at 3.2 K was studied using infrared (IR) spectroscopy. Mixtures of C5H8 and Cl2 were codeposited in p-H2 at 3.2 K, followed by irradiation with ultraviolet light at 365 nm to induce the photodissociation of Cl2 and the subsequent reaction of the Cl atoms with C5H8. Upon 365 nm photolysis, a multitude of new lines appeared in the IR spectrum, and, based on the secondary photolysis behavior, it was determined that the majority of the new lines belong to two distinct chemical species, designated as set A (intense lines at 1237.9, 807.8, and 605.6/608.2 cm-1, and several other weaker lines) and set B (intense lines at 942.4, 1257.7, 796.7/798.5, 667.9, and 569.7 cm-1, and several other weaker lines). Quantum-chemical calculations were performed at the B3PW91/6-311++G(2d,2p) level for ·C5H7 and the four possible isomers of the ·C5H8Cl radicals, produced from the addition of the Cl atom to the four distinct sites of carbon atoms in C5H8, to determine the relative energetics and predict IR spectra for each radical. The newly observed lines of sets A and B are assigned to the 1-chloromethyl-2-methylallyl radical (addition to carbon 4) and the 1-chloromethyl-1-methylallyl radical (addition to carbon 1) according to comparison with predicted IR spectra of possible products. The 1-chloromethyl-2-methylallyl radical and 1-chloromethyl-1-methylallyl radicals were predicted to be the most stable, with the latter ∼8 kJ mol-1 lower in energy than the former. The ratio of the 1-chloromethyl-1-methylallyl to the 1-chloromethyl-2-methylallyl radicals is estimated to be (1.2 ± 0.5):1.0, indicating that the two radicals are produced in approximately equal amounts. The exclusive production of the radicals involving the addition of the Cl atom to the two terminal carbons of isoprene is analogous to what was previously observed for the reaction of Cl atoms with trans-1,3-butadiene in solid p-H2.

Hydrogenation reactions in the N/O chemical network are important for an understanding of the mechanism of formation of organic molecules in dark interstellar clouds, but many reactions remain unknown. We present the results of the reaction H + HONO in solid para-hydrogen (p-H2) at 3.3 K investigated with infrared spectra. Two methods that produced hydrogen atoms were the irradiation of HONO molecules in p-H2 at 365 nm to produce OH radicals that reacted readily with nearby H2 to produce mobile H atoms, and irradiation of Cl2 molecules (co-deposited with HONO) in p-H2 at 405 nm to produce Cl atoms that reacted, upon IR irradiation of the p-H2 matrix, readily with nearby H2 to produce mobile H atoms. In both experiments, we assigned IR lines at 3549.6 (ν1), 1465.0 (ν3), 1372.2 (ν4), 898.5/895.6 (ν6), and 630.9 (ν7) cm-1 to hydroxy(oxido)-λ5-azanyl radical [˙ONH(OH)], the primary product of HONO hydrogenation. Two weak lines at 3603.4 and 991.0 cm-1 are tentatively assigned to the dihydroxy-λ5-azanyl radical, ˙N(OH)2. The assignments were derived according to the consideration of possible reactions and comparison of observed vibrational wavenumbers and their IR intensities with values predicted quantum-chemically with the B3LYP/aug-cc-pVTZ method. The agreement between observed and calculated D/H- and 15N/14N-isotopic ratios further supports these assignments. The role of this reaction in the N/O chemical network in dark interstellar clouds is discussed.

Ultraviolet laser pulses at 355 nm with variable pulse widths in the region from 170 ps to 1.5 ns were used to investigate the ionization mechanism of matrix-assisted laser desorption/ionization (MALDI) for matrices 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA). The mass spectra of desorbed ions and the intensity and velocity distribution of desorbed neutrals were measured simultaneously for each laser shot. These quantities were found to be independent of the laser pulse width. A comparison of the experimental measurements and numerical simulations according to the multiphoton ionization, coupled photophysical and chemical dynamics (CPCD), and thermally induced proton transfer models showed that the predictions of thermally induced proton transfer model were in agreement with the experimental data, but those of the multiphoton ionization model were not. Moreover, the predictions of the CPCD model based on singlet–singlet energy pooling were inconsistent with the experimental data of CHCA and SA, but were consistent with the experimental data of DHB only when some parameters used in the model were adjusted to extreme values.

We recorded infrared (IR) spectra in the CH- and OH-stretching regions of size-selected clusters of methanol (M) with one water molecule (W), represented as MnW, n = 1-4, in a pulsed supersonic jet using the photoionization/IR-depletion technique. Vacuum ultraviolet emission at 118 nm served as the source of ionization in a time-of-flight mass spectrometer to detect clusters MnW as protonated forms Mn-1WH+. The variations in intensities of Mn-1WH+ were monitored as the wavelength of the IR laser light was tuned across the range 2700-3800 cm-1. IR spectra of size-selected clusters were obtained on processing of the observed action spectra of the related cluster-ions according to a mechanism that takes into account the production and loss of each cluster due to IR photodissociation. Spectra of methanol-water clusters in the OH region show significant variations as the number of methanol molecules increases, whereas those in the CH region are similar for all clusters. Scaled harmonic vibrational wavenumbers and relative IR intensities predicted with the M06-2X/aug-cc-pVTZ method for the methanol-water clusters are consistent with our experimental results. For dimers, absorption bands of a structure WM with H2O as a hydrogen-bond donor were observed at 3570, 3682, and 3722 cm-1, whereas weak bands of MW with methanol as a hydrogen-bond donor were observed at 3611 and 3753 cm-1. For M2W, the free OH band of H2O was observed at 3721 cm-1, whereas a broad feature was deconvoluted to three bands near 3425, 3472, and 3536 cm-1, corresponding to the three hydrogen-bonded OH-stretching modes in a cyclic structure. For M3W, the free OH shifted to 3715 cm-1, and the hydrogen-bonded OH-stretching bands became much broader, with a weak feature near 3179 cm-1 corresponding to the symmetric OH-stretching mode of a cyclic structure. For M4W, the observed spectrum agrees unsatisfactorily with predictions for the most stable cyclic structure, indicating significant contributions from branched isomers, which is distinctly different from M5 of which the cyclic form dominates.

With a step-scan Fourier-transform spectrometer we recorded temporally resolved infrared absorption spectra of CH3OO radicals that were produced upon irradiation of CH3COCH3 and O2 at 193 nm in a flowing mixture. At a resolution of 0.15 cm(-1), the rotational structure of the ν2 band of CH3OO near 2954.4 cm(-1) is partially resolved and shows an unexpectedly broadened, and somewhat distorted, Q-branch. A 4D model Hamiltonian, consisting of three CH stretches and the methyl torsion, was developed to explore the origins of this broadening. The vibrational progressions predicted by the model Hamiltonian and the rotational contours of the ν2 band, based on experimental ground-state rotational parameters and their values scaled by their calculated ratios for the upper state, produced simulations in satisfactory agreement with the observed spectrum. These results provide new insight into the vibrational couplings in CH3OO.

In a study of the metal-related ion generation mechanism in matrix-assisted laser desorption ionization (MALDI), crystals of matrix used in MALDI were grown from matrix- and salt-containing solutions. The intensities of metal ion and metal adducts of the matrix ion obtained from unwashed crystals were higher than those from crystals washed with deionized water, indicating that metal ions and metal adducts of the matrix ions are mainly generated from the surface of crystals. The contributions of preformed metal ions and metal adducts of the matrix ions inside the matrix crystals were minor. Metal adducts of the matrix and analyte ion intensities generated from a mixture of dried matrix, salt, and analyte powders were similar to or higher than those generated from the powder of dried droplet crystals, indicating that the contributions of the preformed metal adducts of the matrix and analyte ions were insignificant. Correlation between metal-related ion intensity fluctuation and protonated ion intensity fluctuation was observed, indicating that the generation mechanism of the metal-related ions is similar to that of the protonated ions. Because the thermally induced proton transfer model effectively describes the generation of the protonated ions, we suggest that metal-related ions are mainly generated from the salt dissolution in the matrix melted by the laser.