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Significant efforts have been directed towards the use of transition metal nitrides as electrocatalysts for hydrogen evolution reaction (HER). Molybdenum nitride, despite its promise for scalable production, suffers from the bottleneck of poor catalytic activity. Furthermore the kinetics of water dissociation process ought to be improved for enhancing its potential. Here, we report a facile method for the incorporation of trace amount of Pd nanoparticle into Mo3N2 nanobelts (0.75Pd/Mo3N2,) for enhanced HER in both acidic and alkaline solutions. When employed for HER, the 0.75 wt%Pd/Mo3N2 nanobelt delivers excellent catalytic activity with overpotentials of 45 and65 mV in 0.5 M H2SO4 and 1 M KOH at a current density of 10 mA cm-2. As-prepared 0.75 wt%Pd/Mo3N2 displays a smaller Tafel slope and offers substantial stability in both acidic and alkaline media under the same operating conditions. The improved performance of the as-prepared 0.75 wt%Pd/Mo3N2 points to fast charge transfer, higher electrical conductivity and synergistic effects between Pd and Mo. This work displays a direct method for reducing the use and cost associated with use of platinum-group metals while also delivering superior HER catalytic performance.

Exploring the initial reactions of H-free and nitro-free energetic materials could enrich our understanding into the thermal decomposition mechanism of various energetic materials (EMs). In this work, two furoxan compounds, 3,4-dinitrofurazanfuroxan (DNTF) and benzotrifuroxan (BTF), were investigated to shed light on the decay mechanism of furoxan compounds based on the self-consistent charge density functional tight binding molecular dynamic simulations. Results show that DNTF and BTF decay in a unimolecular mechanism, and the transformation of furoxan ring to nitro group are suggested as a novel initial channel. Five initial steps of DNTF are observed, including NO2 loss and the N(O)-O bond cleavage of central and peripheral rings. The bond cleavage of peripheral rings dominates the decay at low temperature, while the central ring opening and C-NO2 dissociation governs the high temperature decay. Besides, NO2, CO and NO fragments are mainly yield at high temperature, while CO3N2 is dominant at low temperature. The three-stage characteristics of the exothermic of BTF decay are described under programmed heating conditions for the first time. Four initial steps of BTF were identified, including furoxan ring opening reactions and the breakage of 6-membered ring C-C bond. The cleavage of N(O)-O bond rules the initial step of BTF under different heating conditions, and the frequency increased with the temperature increasing. In addition, the amount of CON, ON and CO are higher at high temperature, while C2O2N2 shows a opposite trend. What obtained this work promote deepen insights into the complicated sensitivity mechanism of EMs.

Alkali metals are commonly used to promote heterogeneous catalysts. For instance, K can enhance the MoS2-catalyzed synthesis of methanethiol, an important industrial chemical, from CO/H2/H2S. Herein, we not only demonstrate that the synergy increases with alkali cation size (Cs > Rb > K > Na) but also that alkali sulfides themselves are the active sites. The alkali-normalized methanethiol formation rate of Cs sulfide is nearly the same as that of Cs-promoted MoS2 with a much lower yield of unwanted methane. Kinetic measurements show that methanethiol on alkali sulfides is formed via the reaction 3 CO + 2 H2S → COS + CO2 + CH3SH. This represents a first example of H2S as a hydrogen donor for the formation of the thiol counterpart of methanol. The role of MoS2 is that of a promoter that disperses alkali and provides spillover H from H2 dissociation.

The supported metal catalysts are usually prepared and widely applied in aqueous phase. Here, by performing density functional theory calculations and ab initio molecular dynamics simulations with explicit solvent waters, the metal-support interaction of Pd@ZrO2 catalyst was found to be enhanced by water dissociation at the metal-support interface. This happens to an appreciable number of interfacial waters, generating ∼ 25% hydrides compared to Pd atoms. After the partially heterolytic water dissociation, the generated Hδ+ would undergo the proton coupled electron transfer (PCET) from Pd to form the hydride (Hδ-). The spatial separation of the generated H on Pd and remaining OH on ZrO2 results in the polarization of metal-support interface, which then flattens the shape of cluster. Moreover, the formed metal-hydride behaves as the new catalytic active phase for CO oxidation, making the catalyst highly active in water vapor.

Identifying optimal Ru size in NH3 synthesis can improve reaction activity and maximize the utilization of Ru to reduce catalyst cost. However, previous researches are focused on large Ru particle size (≥ 2 nm) while that below 2 nm in NH3 synthesis is unclear. Here we synthesized a series of Rux/BaCeO3 with different Ru sizes (x=1.1–3.0 nm) through size-controlled Ru colloid. With the decrease of Ru size, NH3 synthesis rate over Ru1.1/BaCeO3 increases to 19.4 mmol gcat−1 h−1 at 400°C and 1 MPa, which is 5.7 times that of Ru3.0/BaCeO3 and superior to most of Ru-based catalysts previously reported. It reveals that the reduction of Ru size enhances the generation of Ce3+ and oxygen vacancies in BaCeO3, which can donate electron to Ru centers and promote N2 dissociation. Moreover, the small Ru size enhances hydrogen spillover from Ru to BaCeO3 to alleviate hydrogen poisoning, resulting in efficient NH3 synthesis.

Interanion hydrogen bonding (IAHB) and halogen bonding (IAXB) have emerged as a counterintuitive linker in a range of fascinating applications. Despite the overall repulsive (positive) binding energy, anions are trapped in a local minimum with its corresponding transition state (TS) preventing dissociation. In other words, the adduct of anions is metastable. Seemingly, the electrostatic paradigm and force field description of hydrogen/halogen bonding (HB/XB) are challenged, because of the preconceived Coulombic repulsion. Aiming at an insightful understanding of these interanion phenomena, we employed the energy decomposition approach based on the block-localized wavefunction method (BLW-ED) to investigate a series of exemplary interanion complexes. As expected, the key distinction from the conventional HB/XB lies in the electrostatic interaction, which is not increasingly repulsive as anions gradually approach to each other. Rather, there is a Coulombic barrier at a certain point. After this point, the electrostatic repulsion diminishes with the decreasing distance between anions. Differently, other energy components vary monotonically just like in conventional cases. The nonmonotonic characteristic of the electrostatic interaction in interanion complexes was reproduced using the multipole expansion in AMOEBA polarizable force field in which the state-specified atomic multipoles were adopted. This suggests that the nonmonotonicity can be well interpreted by classical electrostatic theory and there is no conceptual difference between conventional HB/XB and IAHB/IAXB. The stability of IAHB/IAXB depends on the competition between the local attractive HB/XB and the global Coulombic repulsion of net charges, though there is cooperativity between these two contrasting forces. This concise model was supported by the attractive IAHB/IAXB in modified molecular capsules, which exhibit strong quadruple HB/XBs and a considerable distance between charged substituents.

The photodissociation of methyl hydroperoxide (CH3OOH) at 193 nm has been studied using a direct dynamics trajectory surface-hopping (TSH) method. The potential energies, energy gradients, and nonadiabatic couplings are calculated on the fly at the MRCIS(6,7)/aug-cc-pVDZ level of theory. The hopping of a trajectory from one electronic state to another is decided on the basis of Tully's fewest switches algorithm. An analysis of the trajectories reveals that the cleavage of the weakest O-O bond leads to major products CH3O(2E) + OH(2Π), contributing about 72.7% of the overall product formation. This OH elimination was completed in the ground degenerate product state where both the ground singlet (S0) and first excited singlet (S1) states become degenerate. The O-H bond dissociation of CH3OOH is a minor channel contributing about 27.3% to product formation, resulting in products CH3OO + H. An inspection of the trajectories indicates that unlike the major channel OH elimination, the H-atom elimination channel makes a significant contribution (∼3% of the overall product formation) through the nonadiabatic pathway via conical intersection S1/S0 leading to ground-state products CH3OO(X 2A″) + H(2S) in addition to adiabatic dissociation in the first excited singlet state, S1, correlating to products CH3OO(1 2A') + H(2S). The computed translational energy of the majority of the OH products is found to be high, distributed in the range of 70 to 100 kcal/mol, indicating that the dissociation takes place on a strong repulsive potential energy surface. This finding is consistent with the nature of the experimentally derived translational energy distribution of OH with an average translational energy of 67 kcal/mol after the excitation of CH3OOH at 193 nm.

Scaling relations play a vital role in high-throughput screening of catalytic materials, and more and more attention is being paid to strain-based regulation of catalytic performance. Here we investigated the variation of several energetics, including adsorption energies in the initial state, transition state, and final state, reaction energies, and energy barriers with strain, by studying CO, BH, NH, CH, and NO adsorption and dissociation on M(111) (M = Cu, Ag, Ni, Pd, or Pt) surfaces. We show that energy barriers, reaction energies, and adsorption energies can vary either linearly or nonlinearly (quadratically) with strain. Systems with stronger adsorbate-substrate interaction and weaker atom-atom interaction in substrates are more likely to exhibit nonlinear relations. The well-known Brønsted-Evans-Polanyi relationships and transition state scaling relationships under strain were also examined, and both of them can be nonlinear under strain, in principle. The observed nonlinear relationships were satisfactorily rationalized with the equations derived from Mechanics of Solids.

The magnetic bistability of spin-crossover (SCO) materials is highly appealing for applications as molecular switches and information storage. However, switching of the spin state around room temperature remains challenging. In this work, we reported the successful manipulation of the spin states of two iron(II) complexes (1-Fe and 2-Fe) based on pyridylacylhydrazone ligands in manifold ways. Both complexes are stabilized in the low-spin (LS) state at room temperature because of the strong ligand-field strength imposed by the ligands. 2-Fe shows thermoinduced SCO above room temperature with a very large and reproducible hysteresis (>50 K), while 1-Fe remains in the LS state up to 400 K. Acidity-driven spin-state switching of the two complexes was achieved at room temperature as a result of the complex dissociation and release of iron(II) in its high-spin (HS) state. Recovery of the complex is feasible upon further alkalization treatment in the case of 1-Fe, allowing bidirectional modulation of the spin state of the metal center. Light-driven one-way switching from LS to HS is also achieved by virtue of E-to-Z isomerization at the C═N double bond, which results in dissociation of the complex because of the poor binding affinity in the Z configuration.

Bipolar membranes (BPMs) possess the potential to optimize pH environments for electrochemical synthesis applications when employed in reverse bias. Unfortunately, the performance of BPMs in revers...

Recently, astronomically important silaisocyanoacetylene (HCCNSi) possessing a large dipole moment has been detected for the first time with the help of crossed molecular beam experiments. Quantum chemical computations at higher levels of theory have also been performed to characterize the transient species. In this study, we have analyzed the equilibrium geometry, stability, reactivity, and energetics as well as the nature of bonding in the noble gas (Ng) inserted HCCNSi compound. We have also considered its F analogue to understand the influence of the most electronegative atom in the compound. Metastable behavior of the XNgNSi compounds (X = HCC, F; Ng = Kr-Rn) is examined by calculating thermochemical parameters like free energy change (ΔG) and zero-point-energy-corrected dissociation energy (D0) at 298 K for all possible two-body (2B) and three-body (3B) (both neutral as well as ionic) dissociation channels using coupled-cluster theory [CCSD(T)] in addition to density functional theory (DFT) as well as second order Moller-Plesset perturbation theory (MP2). The set of predicted compounds is found to be endergonic in nature, having high positive free energy change suggesting the thermochemical stability of the compounds except for the 2B Ng-release paths. Though thermodynamically feasible, they are kinetically protected with very high activation free energy barriers. Interestingly, the release of Ng from the parent moiety XNgNSi produces the XSiN isomer, by 180° flipping of the NSi moiety. This can also be seen in the dynamical simulation carried out with the help of atom-centered density matrix propagation (ADMP) technique at 2000K for 1 ps. The bonding in Ng-C, Ng-F, and Ng-N bonds of the studied compounds is analyzed and described with the aid of natural bond orbital (NBO), topological parameters computed using atoms-in-molecules theory (AIM), energy decomposition analysis (EDA), and adaptive natural density partitioning (AdNDP) methods. The natural charge distribution on the constituent atoms suggests that the compounds can be partitioned into both ways of representations, viz., neutral radical as well as ionic fragments. Lastly, the reactivity of the compounds is scrutinized using certain reactivity descriptors calculated within the domain of conceptual density functional theory (CDFT).

We present the photoinduced size/structure transformation of [Au37-xAgx(PPh3)13Cl10]3+ (M37) into [Au25-yAgy(PPh3)10Cl8]+ (M25) cluster. Single-crystal X-ray diffraction revealed that M37 has a tri-icosahedron M36 metal core assembled via the fusion of three Au7Ag6 icosahedrons in a cyclic fashion and that the M36 core is further protected by phosphine and chloride ligands. The M37 cluster is found to be highly sensitive toward ambient light, and the M37 → M25 transition is observed with 530 nm irradiation, monitored by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and femtosecond transient absorption spectroscopy. Linear-response time-dependent DFT calculations indicated that the strong absorption of the M37 cluster close to 500 nm induces an antibonding-type configuration in the induced electron density within the plane of the three 8-electron systems, possibly promoting dissociation of one of the 8-electron superatoms. This theoretical result supports the experimental observation of the sensitivity of the M37 → M25 transition to 530 nm irradiation.

The charge density distribution in a novel cocrystal (1) complex of 1,3-dimethylxanthine (theophylline) and propanedioic acid (malonic acid) has been determined. The molecules crystallize in the triclinic, centrosymmetric space group P1̅, with four independent molecules (Z = 4) in the asymmetric unit (two molecules each of theophylline and malonic acid). Theophylline has a notably high hygroscopic nature, and numerous cocrystals have shown a significant improvement in stability to humidity. A charge density study of the novel polymorph has identified interesting theoretical results correlating the stability enhancement of theophylline via cocrystallization. Topological analysis of the electron density highlighted key differences (up to 17.8) in Laplacian (∇2ρ) between the experimental (EXP) and single-point (SP) models, mainly around intermolecular-bonded carbonyls. Further investigation via molecular electrostatic potential maps reaffirmed that the charge redistribution enhanced intramolecular hydrogen bonding, predominantly for N(2′) and N(2) (61.2 and 61.8 kJ mol–1, respectively). An overall weaker lattice energy of the triclinic form (−126.1 kJ mol–1) compared to that of the monoclinic form (−133.8 kJ mol–1) suggests a lower energy threshold to overcome to initiate dissociation. Future work via physical testing of the novel cocrystal in both dissolution and solubility will further solidify the correlation between theoretical and experimental results.

Values of the standard enthalpies of formation D,L-alanyl-D,L-serine are calculated using additive groups approach based on group systematics with such classifications of fragments as the Benson classification, which considers the effect of the primary environment of atoms. The heat effects of the dissolution of crystalline D,L-alanyl-D,L-serine in water and in solutions of potassium hydroxide at 298.15 K are determined via direct calorimetry in a wide range of concentrations. The standard enthalpies of formation of the peptide and products of its dissociation in an aqueous solution are calculated.

The journal of physical chemistry / A 125, 10138���10143 (2021). doi:10.1021/acs.jpca.1c06033, We performed a time-resolved spectroscopy experixment on the dissociation of oxygen molecules after the interactionwith intense extreme-ultraviolet (XUV) light from the free-electronlaser in Hamburg at Deutsches Elektronen-Synchrotron. Using anXUV-pump/XUV-probe transient-absorption geometry with asplit-and-delay unit, we observe the onset of electronic transitionsin the O$^{2+}$ cation near 50 eV photon energy, marking the end ofthe progression from a molecule to two isolated atoms. We observetwo different time scales of 290 �� 53 and 180 �� 76 fs for theemergence of different ionic transitions, indicating differentdissociation pathways taken by the departing oxygen atoms.With regard to the emerging opportunities of tuning the centralfrequencies of pump and probe pulses and of increasing the probe���pulse bandwidth, future pump���probe transient-absorptionexperiments are expected to provide a detailed view of the coupled nuclear and electronic dynamics during molecular dissociation, Published by Soc., Washington, DC

While forward and reverse rate constants are frequently used to determine enthalpies of reaction and formation, this process is more difficult for pressure-dependent association/dissociation reactions, especially since the forward and reverse reactions are usually studied at very different temperatures. The problems can be overcome by using a data-fitting procedure based on a master equation model. This approach has been applied to existing experimental pressure-dependent forward and reverse rate coefficients for the reaction C2H4 + H ⇄ C2H5 (k1, k-1) using the MESMER code to determine ΔfH0⊖C2H5 from the enthalpy of the reaction. New measurements of k1, k-1 were included in analysis. They are based on laser flash photolysis with direct observation of H atom time profiles by vacuum ultraviolet laser-induced fluorescence under conditions where the approach to equilibrium could be observed. Measurements were made over the temperature range 798-828 K and with [He] from 2.33 to 7.21 × 1018 molecule cm-3. These data were then combined with a wide range of existing experimental data with helium as the bath gas (112 measurements of k1 and k-1, covering the temperature range 285-1094 K, and [He] = 7.1 × 1015-1.9 × 1019 molecule cm-3) and fitted using the master equation solver MESMER. The required vibrational frequencies and rotational constants of the system were obtained from ab initio calculations, and the activation threshold for association (ΔEthresh), enthalpy of reaction (ΔrH0⊖), imaginary frequency (υimag), and helium energy-transfer parameters (⟨ΔE⟩d,298(T/298)n) were optimized. The resulting parameters (errors are 2σ) are ΔEthresh = 11.43 ± 0.34 kJ mol-1, ΔrH0⊖ = -145.34 ± 0.60 kJ mol-1, υimag = 730 ± 130 cm-1, ⟨ΔE⟩d,298 = 54.2 ± 7.6 cm-1, and n = 1.17 ± 0.12. A value of ΔfH298.15⊖(C2H5) = 120.49 ± 0.57 kJ mol-1 is obtained by combining ΔrH0⊖ with standard enthalpies of formation for H and C2H4 and making the appropriate temperature corrections. The dependence of these parameters on how the internal rotor and CH2 inversion modes are treated has been explored. The experimental data for other bath gases have been analyzed, and data sets compatible with the potential energy surface parameters determined above have been identified. The parameters are virtually identical but with slightly smaller error limits. Parameterization of k1, k-1 using the Troe formalization has been used to investigate competition between ethyl decomposition and reaction with oxygen under combustion conditions.

Dissociation of a ligand isoniazid from a protein catalase was investigated using all-atom molecular dynamics (MD) simulations. Random acceleration MD (τ-RAMD) was used, in which a random artificial force applied to the ligand facilitates its dissociation. We have suggested a novel approach to extrapolate such obtained dissociation times to the zero-force limit assuming never before attempted universal exponential dependence of the bond strength on the applied force, allowing direct comparison with experimentally measured values. We have found that our calculated dissociation time was equal to 36.1 s with statistically significant values distributed in the interval of 0.2-72.0 s, which quantitatively matches the experimental value of 50 ± 8 s despite the extrapolation over 9 orders of magnitude in time.

Ligand substitution at the metal center is common in catalysis and signal transduction of metalloproteins. Understanding the effects of particular ligands, as well as the polypeptide surrounding, is critical for uncovering mechanisms of these biological processes and exploiting them in the design of bioinspired catalysts and molecular devices. A series of switchable K79G/M80X/F82C (X = Met, His, or Lys) variants of cytochrome (cyt) c was employed to directly compare the stability of differently ligated proteins and activation barriers for Met, His, and Lys replacement at the ferric heme iron. Studies of these variants and their nonswitchable counterparts K79G/M80X have revealed stability trends Met < Lys < His and Lys < His < Met for the protein FeIII-X and FeII-X species, respectively. The differences in the hydrogen-bonding interactions in folded proteins and in solvation of unbound X in the unfolded proteins explain these trends. Calculations of free energy of ligand dissociation in small heme model complexes reveal that the ease of the FeIII-X bond breaking increases in the series amine < imidazole < thioether, mirroring trends in hardness of these ligands. Experimental rate constants for X dissociation in differently ligated cyt c variants are consistent with this sequence, but the differences between Met and His dissociation rates are attenuated because the former process is limited by the heme crevice opening. Analyses of activation parameters and comparisons to those for the Lys-to-Met ligand switch in the alkaline transition suggest that ligand dissociation is entropically driven in all the variants and accompanied by Lys protonation at neutral pH. The described thiolate redox-linked switches have offered a wealth of new information about interactions of different protein-derived ligands with the heme iron in cyt c model proteins, and we anticipate that the strategy of employing these switches could benefit studies of other redox metalloproteins and model complexes.

High-quality solid electrolyte is the key to developing high-performance all-solid-state lithium-metal batteries (ASSLMBs). Herein, we report a thin composite polymer electrolyte (CPE) based on nanosized Li6.4La3Zr1.4Ta0.6O12 (N-LLZTO) and the PVDF-HFP matrix through a simple film-casting method. N-LLZTO induces partial dehydrofluorination of the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix that activates the coordination of Li+ with PVDF-HFP and LLZTO due to Lewis acid-base interactions, which facilitates dissociation of lithium salt to increase the Li+ carrier density. As a result, the as-fabricated composite polymer electrolyte with a 20 wt % N-LLZTO (CPE-20) membrane possesses high ionic conductivity (1.7 × 10-4 S cm-1), a high lithium-ion transference number (0.57), a wide electrochemical window (∼4.8 V), and good thermal stability. Moreover, the CPE-20 membrane displays excellent electrochemical stability to suppress the lithium dendrite and serves more than 2000 h. The solid-state Li|CPE-20|LiFePO4 pouch cells exhibit excellent cycling and rate performance, as well as high energy density. This study presents an effective strategy to design promising solid-state electrolyte for next-generation ASSLMBs.

Mass spectra of n-pentane and n-hexane ionized through femtosecond-laser pulses were measured using a time-of-flight mass spectrometer. Fragment ions ejected with large kinetic energies were identified as side peaks in which a two-body dissociation pathway, C5H12++ → C2H5+ + C3H7+, was identified for n-pentane, and two for n-hexane, C6H14++ → C2H5+ + C4H9+ and C3H7+ + C3H7+, based on momentum matching of the fragments. The two-body dissociation pathways were observed when the polarization direction of the linearly polarized laser light was perpendicular to the molecular axis. However, when the polarization direction was parallel to the molecular axis or the laser light was circularly polarized, these signals were weak or difficult to identify. These results suggest that the two-body dissociation pathways are caused by nonsequential double ionization (NSDI), which begins with ionization from the π-type second highest occupied molecular orbital (HOMO-1) via the laser electric field perpendicular to the molecular axis rather than bonding the σ-type HOMO. Quantum chemical calculations show that the dication has a triplet metastable state with the same formula as the neutral state (i.e., 3[CH3-(CH2)n-CH3]++). Therefore, the relevant two-body dissociation channels open through transition states with the (HOMO)1(HOMO-1)1 electron configuration and the estimated kinetic energy release values correlate with those observed.

Association and dissociation of proteins are important biochemical events. In this Feature Article, we analyze the available studies of these processes for insulin oligomers in aqueous solution. We focus on the solvation of the insulin monomer in water, stability and dissociation of its dimer, and structural integrity of the hexamer. The intricate role of water in solvation of the dimer- and hexamer-forming surfaces, in long-range interactions between the monomers and the stability of the oligomers, is discussed. Ten water molecules inside the central cavity stabilize the structure of the insulin hexamer. We discuss how different order parameters can be used to understand the dissociation of the insulin dimer. The calculation of the rate using a recently computed multidimensional free energy provides considerable insight into the interplay between protein and water dynamics.

Understanding the separation of the correlated triplet pair state 1(TT) intermediate is critical for leveraging singlet fission to improve solar cell efficiency. This separation mechanism is dominated by two key interactions: (i) the exchange interaction (K) between the triplets which leads to the spin splitting of the biexciton state into 1(TT),3(TT) and 5(TT) states, and (ii) the triplet-triplet energy transfer integral (t) which enables the formation of the spatially separated (but still spin entangled) state 1(T···T). We develop a simple ab initio technique to compute both the biexciton exchange (K) and biexciton transfer coupling. Our key findings reveal new conditions for successful correlated triplet pair state dissociation. The biexciton exchange interaction needs to be ferromagnetic or negligible to the triplet energy transfer for favorable dissociation. We also explore the effect of chromophore packing to reveal geometries where these conditions are achieved for tetracene.

International audience; A series of multicomponent glasses containing up to five oxides are studied using classical molecular dynamics simulations and neutron scattering experiments. The focus is on the role of magnesium in determining the structural properties of these glasses and the possible mixed effect during a sodium/magnesium substitution. Calculated structure functions (pair correlation function and structure factor) rather accurately reproduce their experimental counterpart, and we show that more fine structural features are qualitatively reproduced well, despite some discrepancies in the preferential spatial distribution between sodium and magnesium to aluminum and boron, as well as the nonbridging oxygen, distribution. The simulated systems offer a solid basis to support previous experimental findings on the composition–structure relationship, allowing for further analysis and property calculation. It is confirmed that the substitution of sodium by magnesium leads to the decrease of four-fold boron and a modification of the alkali coordinations with a significant change of the network structure. Specifically, magnesium coordination extracted from numerical simulations highlights a potential dissociation from penta- to tetra- and hexahedral units with increasing MgO contents along the glass series, which could not be resolved experimentally.

Photodissociation dynamics of the jet-cooled vinoxy radical (CH2CHO) via the B2A″ state was studied in the near-ultraviolet (near-UV) region of 308-328 nm using high-n Rydberg H atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The vinoxy radical beam was produced by 193 nm photolysis of ethyl vinyl ether followed by supersonic expansion. The H + CH2CO product channel was observed directly in the H atom TOF spectra. The H atom photofragment yield (PFY) spectra were obtained by integrating the H atom TOF spectra and measuring the H atom REMPI signals, and showed several vibronic bands of the B2A″ state. The translational energy distributions of the H + CH2CO products, P(ET)'s, were obtained at several vibronic transitions. The P(ET) distributions were broad, peaking at a low energy of ∼3500 cm-1. The product translational energy release was moderate; the average translational energy release in the maximum available energy, ⟨fT⟩, was in the range of 0.24-0.27. The product angular distributions in this wavelength region were slightly anisotropic, with the β parameter in the range of 0.10-0.24. The near-UV photodissociation mechanism of the H + CH2CO product channel of the vinoxy radical is consistent with unimolecular dissociation on the electronic ground state (X2A″) following internal conversion from the B2A″ state to the A2A' state and then to the X2A″ state (although unimolecular dissociation from the first excited A2A' may also contribute).

The dissociation of O2 molecules chemisorbed on silver surfaces is an essential reaction in industry, and the dissociation mechanism has long attracted attention. The detailed dissociation mechanism was studied at the single-molecule level on Ag(110) by using a scanning tunneling microscope (STM). The dissociation reaction was found to be predominantly triggered by inelastically tunneled holes from the STM tip due to the significantly distributed density of states below the Fermi level of the substrate. A combination of action spectroscopy with the STM and density functional theory calculations revealed that the O2 dissociation reaction is caused by direct ladder-climbing excitation of the high-order overtones of the O-O stretching mode arising from anharmonicity enhanced by molecule-surface interactions.

Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis of ketene from acetic acid over the (3,0;1,1) surface of Cu2O(1 0 0) through analysis of the adsorption and desorption characteristics of formic and acetic acids. The results allow us to establish a reaction mechanism for ketene formation. Observations from x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, and temperature programmed desorption (TPD), supported by a comparison with formic acid results, suggest that acetic acid reacts with Cu2O through deprotonation to form acetate species coordinated to copper sites and hydroxylation of nearby surface oxygen sites. For formic acid the decomposition of adsorbed formate species results in desorption of CO2 and CO while, for acetic acid, high yields of ketene are observed at temperature >500 K. Modeling by density functional theory (DFT) confirms the strong interaction of acetic acid with the (3,0;1,1) surface and the spontaneous dissociation into adsorbed acetate and hydrogen atom species, the latter forming an OH-group. In an identified reaction intermediate ketene binds via all C and O atoms to Cu surface sites, in agreement with interpretations from XPS. In the vicinity of the adsorbate the surface experiences a local reorganization into a c(2 × 2) reconstruction. The total computed energy barrier for ketene formation is 1.81 eV in good agreement with the 1.74 eV obtained from TPD analysis. Our experimental observations and mechanistic DFT studies suggests that Cu2O can operate as an efficient catalyst for the green generation of ketene from acetic acid., Swedish Research Council (VR); VR Starting Grant; Knut och Alice Wallenbergs stiftelse; STINT Joint China-Sweden Mobility Program; Ragnar Holm Foundation; Trygger’s Foundation; Chalmers Areas of Advance-Materials Science

Calorimetry is used to measure the heats of interaction between an L-glutathione solution and HNO3 solutions at a temperature of 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 М (KNO3 background electrolyte). Literature data on the stepwise dissociation constants of L-glutathione are extrapolated to zero ionic strength. Values $${\text{p}}K_{1}^{0}$$ = 2.05 ± 0.03, $${\text{p}}K_{2}^{0}$$ = 3.49 ± 0.03, $${\text{p}}K_{3}^{0}$$ = 8.65 ± 0.05, and $${\text{p}}K_{4}^{0}$$ = 9.60 ± 0.05 are obtained and the stepwise peptide ionization constants at fixed ionic strength values are calculated (I = 0.5, 1.0, 1.5 М). The values of the heat of dissociation of the tripeptide are calculated using the universal HEAT program. Standard thermodynamic characteristics (ΔrH°, ΔrG°, and ΔrS°) of reactions of acid–base interaction in L-glutathione aqueous solutions are calculated. The effect the concentration of the background electrolyte has on the enthalpy of peptide dissociation is considered.

In an effort to probe the impacts of speciation on spin-state switching, the synthesis and unique solution-phase magnetic properties of [((TIPSC≡C)3tren)Fe(OTf)2] (1) are described. Analysis of the single-crystal X-ray diffraction data shows that the tris(iminoalkyne) ligand coordinates to the iron(II) center through all four nitrogen atoms, while the other two coordination sites are filled by the oxygen atoms from triflate anions. Solid-state variable-temperature (VT) magnetic studies show that 1 remains high-spin (HS) at all temperatures. In the presence of moderately strong coordinating solvents, solvent replaces the two bound triflate counteranions, as observed by 19F NMR spectroscopy and supported by conductivity measurements. VT solution measurements show 1 to be in the HS state when this solvent is oxygen-donating but low-spin (LS) with a nitrogen-donating solvent. In the noncoordinating solvent dichloromethane, both triflates are bound to the iron(II) center at room temperature, but upon cooling, 1 undergoes a coordination change, resulting in the loss of one triflate, as shown by 19F NMR. With the moderately coordinating solvent acetone, triflate dissociation upon cooling results in a spin-switching species with a T1/2 value of 171 K, characterized via 19F NMR, Evans' method, and solution magnetometry measurements. Solution magnetic measurements collected in structurally similar cyclopentanone suggest that the spin-state switching event is exclusive to the acetone environment, suggesting the influence of both the local coordination environment and aggregation. Additionally, a comparison of the solvodoynamic diameters via dynamic light scattering suggests that aggregation of 1 is significantly different in (CH3)2CO and (CD3)2CO, leading to the observation of spin-switching behavior in the former and fully HS behavior in the latter. This study highlights the sensitivity of solution magnetic properties to solvent choice.

Proton-coupled electron transfer (PCET) reactions on metal oxides require coupling between proton transfer at the solid-liquid interface and electron transfer involving defects at or near the band edge. Herein, hybrid functional periodic density functional theory is used to elucidate the impact of proton-coupled defects on the bond dissociation free energies (BDFEs) of O-H bonds on anatase TiO2 surfaces. These O-H BDFEs are directly related to interfacial PCET thermochemistry. Comparison between geometrically similar O-H bonds associated with different defect types, namely conduction d-band electrons or valence p-band holes, reveals that the BDFEs differ by ∼81 kcal/mol (3.50 eV), comparable to the wide TiO2 band gap. These differences are shown to be determined primarily by differences in electron transfer driving forces, which are analyzed by using band energies and inner-sphere reorganization energies within a Marcus theory framework. These fundamental insights about the impact of proton-coupled defects on PCET thermochemistry at semiconductor surfaces have broad implications for electrocatalysis.

A study on the kinetics of the reaction between cyanocobalamin (vitamin B12, CNCbl) and the reduced form of flavin mononucleotide (FMNH2) in weakly acidic, neutral, and slightly alkaline media is performed. It is shown that FMNH2 can reduce CNCbl to cobalamin(II) (Cbl(II)). It is established that protonated, mono-deprotonated, and di-deprotonated forms of FMNH2 can participate in the reaction. The reaction mechanism includes the slow substitution of the 5,6-dimethylbenzimidazole nucleotide with FMNH2 molecule, rapid electron transfer from FMNH2 to Co(III) ions, and the subsequent dissociation of cyanide. The reaction is reversible, due to the ability of the oxidized form of FMNH2 (FMN) to react with the Cbl(II) complex.

Values are presented of the change in the enthalpy of dissociation of glycylglycine and glycine in aqueous solutions of dimethylsulfoxide of various compositions, calculated using the enthalpies of resolvation of participants in acid–base interactions in a water–dimethylsulfoxide solvent. A comparison of the calculated values of the enthalpy of dissociation of glycine in water–dimethylsulfoxide solutions and ones obtained experimentally show good convergence of the results. Values of the change in the entropy of the dissociation of glycylglycine and glycine in aqueous solutions of dimethylsulfoxide are calculated and used to show that the enthalpy and entropic contributions to the change in the Gibbs energy of the considered reactions in water–dimethylsulfoxide mixtures largely compensate for each other.

Investigation of the process of the NO3- anion solvation is central to understanding the chemical and physical properties of its aqueous solutions. The importance of this topic can be seen in atmospheric chemistry, as well as in nuclear waste processing research. In this work, we used a particle swarm optimization technique driven by density functional theory to sample the potential energy surface of various microsolvated [NO3·(H2O)n]- (n = 1-12) clusters. We found that the charge transfer plays a crucial role in the stabilization of the investigated species. Moreover, by conducting ab initio molecular dynamics simulations, we showed that at low concentrations (∼0.2 M) the NO3- species tend to be located on the surface of water solution. We also observed that the contact ion pair K+-NO3- undergoes a fast dissociation and each of the ions is solvated separately. As a result, from our calculations, we expect that at low concentration there could be oppositely signed concentration gradients for NO3- and K+ ions in a thin water film.

Two-dimensional hybrid organic-inorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However, n = 1 two-dimensional (2D) HOIPs face the challenge of low conductivity between the inorganic layers, leading to unsatisfactory device performance. Interestingly, 2D HOIPs employing π-conjugated molecules as organic moieties show energy and charge transfers between organic and inorganic layers, indicating potentially efficient carrier transport for photovoltaic applications. Nevertheless, the development of 2D HOIP-based solar cells especially utilizing polycyclic aromatic alkylammonium as cations is in its infancy. Herein, we investigated the electronic structure and band alignment of a series of n = 1 2D Ruddlesden-Popper (RP) phase HOIPs containing different polycyclic aromatic groups and alkyl chains, based on density functional theory calculations. We find that the polycyclic aromatic group plays an important role in controlling the functionality of 2D HOIPs by directly modifying band-edge states, and the band alignment at the organic-inorganic interface can be designed to promote either exciton trapping or dissociation for light-emitting or photovoltaic applications, respectively.

Detonation energy of novel cyclo-N5--based nitrogen-rich energetic salts is expected to exceed 3 times the equivalent of TNT. PHAC([(N5)6(H3O)3(NH4)4Cl]) was selected as the prototype to investigate the thermal decomposition reaction of PHAC in the solid phase for the first time by the first-principles molecular dynamics method. At about 38 ps, the final state of the reaction was reached. It was found that there were mainly five final products, among which the proportion of N2 molecules was the maximum and accounted for 60% (mole fraction) of all final products. The reaction pathways of PHAC were analyzed, and more than 30 elementary reactions were found. The initial reaction of the PHAC thermal decomposition was the ring-opening of cyclo-N5- ion and proton transfer. The energy release of PHAC thermal decomposition is divided into two stages. The first stage is a slow release of energy before the formation of the HN3 molecule. The second stage is the rapid release of energy after the formation of HN3 molecules. The HN3 molecule is an essential junction, and the unimolecular dissociation of HN3 is the rate-determining step. Such an understanding of reaction mechanism and energy release law greatly promotes the application and synthesis of novel cyclo-N5--based nitrogen-rich energetic salts.

This paper presents the reaction mechanism, cross sections, and product energy partitioning for the O + CO2 reaction, calculated using Born-Oppenheimer molecular dynamics simulations with the quasiclassical trajectory (BOMD-QCT) method. At collision energies up to 9.5 eV, three reactions, oxygen exchange (above ∼1.5 eV), abstraction (above ∼5.5 eV), and dissociation (above ∼7.5 eV) occur, with abstraction and dissociation involving either an insertion-elimination mechanism or a stripping mechanism. The insertion-elimination mechanism involves the formation of a planar CO3 intermediate which lies 0.52 eV above the ground-state CO2; the energetic barrier for oxygen abstraction via this mechanism is 3.52 eV. Interestingly, the insertion-elimination mechanism predominately contributes to the cross sections at collision energies just above the effective energetic threshold for the abstraction and dissociation reactions; at higher collision energies, the contribution from the stripping mechanism increases and eventually dominates. At a collision energy of 9.5 eV, the cross sections for oxygen exchange, abstraction, and dissociation are 4.17 a02, 1.58 a02, and 0.68 a02, respectively. The lower reaction cross sections, higher effective reaction barrier, and product energy distribution of the stripping mechanism were attributed to the short lifetime (28 fs) of the OCOO species compared with that of the CO3 species (45 fs) that arises in the insertion-elimination mechanism. For the exchange reaction, it is found that roughly 40% of the reactant translational energy ends up in CO2 vibration, which provides a single-collision mechanism to produce highly excited CO2. We also studied intersystem crossing effects using trajectory surface hopping calculations and find no changes compared to single surface (triplet) calculations at energies below 7.5 eV; however, at 7.5 eV and higher the abstraction cross sections are changed by as much as 20%, and the (very small) dissociation cross sections are changed by factors of four or more.

The effect of water molecule on the excited states of CH3Cl(H2O), as compared to those of the isolated chloromethane, has been studied at the multireference configuration interaction with singles and doubles (MR-CISD), including extensivity corrections. Eight new Rydberg states are due to the water molecule but the common states of both systems are not severely altered. Potential energy curves of 23 singlet states along the C-Cl coordinate have also been computed at the MR-CISD level. The dissociation energy of the C-Cl bond decreases from ∼0.4 to 0.5 eV due to the water molecule. As for CH3Cl (de Medeiros, V. C., J. Am. Chem. Soc. 2016, 138, 272-280), a stable ion-pair has also been characterized. However, for CH3Cl(H2O), this ion-pair is better described as a solvent-shared semi-ion-pair, CH3+δ(H2O)Cl-δ. This species is connected with three ionic dissociation channels, with two being due to the water molecule. The presence of these new ionic channels, particularly the lowest energy one, [H3C-O]+ + Cl-, raises a very important question of atmospheric relevance: can the interaction of chloroalkanes with water decrease its deleterious effect on the ozone layer? Several potentially new competing dissociation channels are also studied. The latter results can help to set up the most important states to be included in nonadiabatic dynamic calculations to study how the yields of the ionic channels change due to the water molecule.

The research established the regularities for the separation of phenylalanine aqueous salt solutions by electrodialysis. It also determined the conditions for the effective and selective isolation of the target component by selecting a membrane with the desired properties. The composition of the model solution simulating industrial water in the technology of microbiological synthesis included an aromatic amino acid, phenylalanine (0.05 M), and sodium chloride (0.01 M). Experimental membranes with different mass fractions of sulfonated cation-exchange resin were used. Heterogeneous ion-exchange membranes were obtained by hot rolling of a homogenised mixture of a crushed ion-exchanger and polyethylene. The transport characteristics and features of the transfer of components of different nature through the experimental membranes were studied in a galvanostatic mode using a seven-section electrodialyser which was horizontally oriented. It was established that the content of the ion exchanger in the membrane influences the features of the transport of mineral salt and amino acid ions, the value of the separation factor, and the degree of solutions demineralization. It was shown that the change in the content of the sulfonated cation-exchanger in the membranes from 45 to 70 wt.% during the electrodialysis of a mixed solution of an amino acid and a mineral salt makes it possible to increase the rate of mass transfer of a mineral ion by 1.5 times. For all experimental membranes, the separation factor dependences are characterised by extrema corresponding to the interval exceeding the limiting diffusion current ilim by 2-3 times. The maximum separation efficiency was set for a cation exchange membrane with a 70% content of resin. It was found that when the limiting diffusion current was exceeded by a factor of 2 while the content of resin in the membrane increased, the separation factor increased by 1.5 times. Additionally, the degree of demineralization of the solution for the membrane with the maximum content of the ion exchanger was 40-60%. The possibility of almost complete demineralization of the solution for the membrane with a content of resin of 70 wt.% was established when the maximum current was exceeded by 6 times. The study revealed the role of electroconvection in the increase in the loss of the target product of the amino acid with overlimiting current modes of electrodialysis. It was shown that the main reason for the increase in the transfer of amino acids through the sulphonated cation-exchange membrane in intense current modes is the electroconvective mixing of the solution at the interface, which negatively affects the process of water dissociation and destroys the barrier effect of the near-membrane layers of the solution with a high pH value. The research established the possibility of deep demineralization of phenylalanine aqueous salt solution with a loss of the target product of no more than 0.2% using a membrane with a mass fraction of a sulfonated cation-exchange resin of 70 wt.% in intense current modes.

The adhesion and fracture behavior of tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM)/4,4'-diaminodiphenyl sulfone (44DDS)-bisphenol A diglycidyl ether (DGEBA)/44DDS layer interfaces were investigated by molecular dynamics (MD) simulation, mainly focusing on the role of covalent and noncovalent interactions. To accurately investigate the bond dissociation processes, the force field parameters of several bond potentials of the epoxy resin polymers were optimized by density functional theory calculations. In the MD simulations under a tensile load, small voids gradually developed without covalent bond dissociation in the plateau region. In the final large strain region, the stress rapidly increased with bond breaking, leading to failure. When the chemical bonds across the interface between the two layers were removed, the stress-strain curve in the initial elastic region was almost the same as that with interfacial bonds. This showed that the nonbonded interactions governed adhesion strength in the initial elastic region. In contrast, the bonded interactions at interfaces played important roles in the hardening regions because the bonded interactions made the major contribution to the fracture energies. We also investigated the effect of the etherification reaction in cross-linking. It was found that the etherification reaction mainly contributed to the behavior in the late region with large strain. These simulation results revealed that the nonbonded interactions, especially, van der Waals interactions, are important factors for adhesion of the different polymer layers in the small strain region up to the yield point.

Iron-sulfur clusters play important roles in biology as parts of electron-transfer chains and catalytic cofactors. Here, we report a detailed computational analysis of a structural model of the simplest natural iron-sulfur cluster of rubredoxin and its cationic counterparts. Specifically, we investigated adiabatic reduction energies, dissociation energies, and bonding properties of the low-lying electronic states of the complexes [Fe(SCH3)4]2-/1-/2+/3+ using multireference (CASSCF, MRCISD), and coupled cluster [CCSD(T)] methodologies. We show that the nature of the Fe-S chemical bond and the magnitude of the ionization potentials in the anionic and cationic [Fe(SCH3)4] complexes offer a physical rationale for the relative stabilization, structure, and speciation of these complexes. Anionic and cationic complexes present different types of chemical bonds: prevalently ionic in [Fe(SCH3)4]2-/1- complexes and covalent in [Fe(SCH3)4]2+/3+ complexes. The ionic bonds result in an energy gain for the transition [Fe(SCH3)4]2- → [Fe(SCH3)4]- (i.e., FeII → FeIII) of 1.5 eV, while the covalent bonds result in an energy loss for the transition [Fe(SCH3)4]2+ → [Fe(SCH3)4]3+ of 16.6 eV, almost half of the ionization potential of Fe2+. The ionic versus covalent bond character influences the Fe-S bond strength and length, that is, ionic Fe-S bonds are longer than covalent ones by about 0.2 A (for FeII) and 0.04 A (for FeII). Finally, the average Fe-S heterolytic bond strength is 6.7 eV (FeII) and 14.6 eV (FeIII) at the RCCSD(T) level of theory.

Supported bimetallic catalysts of (Co + Pd)/SiO2 system were studied in carbon monoxide hydrogenation. Comparative analysis showed that depending on precursor treatment mode the catalysts ranged in different rows of activity in CO conversion and selectivity to methane. Samples of best performance were obtained after pretreatment in Ar flow. Highly selective catalysts were synthesized by reduction at 450 °C determining low metal dispersion, high extent of alloying, and agglomeration. A low H2,100C/COstrong adsorbed gas ratio was ascribed to a great amount of bimetallic particles and concerned with a diminished number of sites for multiply bonded CO species. Metal dispersion was low due to large Co particles, which enhanced CO dissociation and hydrogenation to CH4. In presence of bimetallic particles the reaction CO + 3H2 = CH4 + H2O was hampered. A decreased H2O formation influenced the WGS reaction. Catalyst samples activated at higher temperatures had better selectivity. During the process, formation of bidentate carbonate species was registered. It was supposed that palladium impeded creation of the latter species and following decomposition to CO2. Active catalyst samples were prepared by reduction at 300 °C leading to higher unreduced cobalt quota and metal dispersion, and decreased alloy particle formation. Higher H2,100C/COstrong ratio values were assigned to pure Co and Pd particle segregation, i.e. availability of sites for multiply bonded CO species favoring a higher activity in CO dissociation and further hydrogenation. A higher amount of CO species on these samples was conducive to CH4 formation, but also to CO2 production. The latter reaction was facilitated by unreduced cobalt.

Yttrocene derivatives [Cp*2Y(MMe4)] (Cp* = C5Me5; M = Al, Ga) and Cp*2Y[Me3Al{B(NDippCH)2}] (Dipp = C6H3iPr2-2,6) deprotonate benzene at elevated temperatures via the release of methane. The formation of [Cp*2Y(Me2MPh2)] (M = Al, Ga), Cp*2Y(MPh4) (M = Al, Ga), Cp*2Y[Me2AlPh{B(NDippCH)2}], and Cp*2Y[AlPh3{B(NDippCH)2}] can be controlled via the temperature applied. The activation temperature and formation of the coordinatively unsaturated "reactive" [Cp*2YMe] strongly depend on the coordination strength of the displaceable Lewis acids [AlMe3]2, GaMe3, and [Me2Al{B(NDippCH)2}]2. Hence, [Cp*2Y(AlMe4)] requires temperatures above 100 °C to metalate benzene, while Cp*2Y[AlMe3{B(NDippCH)2}] undergoes C-H-bond activation even at ambient temperatures. A kinetic deuterium isotope effect was observed for the reactions in C6D6 solutions. Distinct differences in the stabilities of the bulky Group 13 anions ([Me2MPh2]-, [MPh4]-, [Me3Al{B(NDippCH)2}]-, [Me2AlPh{B(NDippCH)2}]-, and [AlPh3{B(NDippCH)2}]-) are assessed by detailed studies of the coordination chemistry with tetrahydrofuran (THF) and by variable-temperature 1H NMR spectroscopy. Thus, increased steric bulk or a reduced Lewis acidity of the Group 13 metal center promote temperature-sensitive dissociation of trivalent Group 13 alkyl entities. Consequently, compound Cp*2Y[AlPh3{B(NDippCH)2}] was found to engage in a dissociation equilibrium with [Cp*2YPh] and AlPh2{B(NDippCH)2} in a C6D6 solution at ambient temperature. The reaction of Cp*2Y[AlPh3{B(NDippCH)2}] with THF results in the concomitant formation of monometallic Cp*2YPh(THF) and the solvent-separated ion pair [Cp*2Y(THF)2][AlPh3{B(NDippCH)2}].

Bromoacetaldehyde (BrCH2CHO) is a major stable brominated organic intermediate of the bromine-ethylene addition reaction during the arctic bromine explosion events. Similar to acetaldehyde, which has been recently identified as a source of organic acids in the troposphere, it may be subjected to photo-tautomerization initially forming brominated vinyl compounds. In this study, we investigate the unimolecular reactions of BrCH2CHO under both photolytic and thermal conditions using high-level quantum chemical calculations and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation analysis. The unimolecular decomposition of BrCH2CHO takes place through 14 dissociation and isomerization channels along a potential energy surface involving eight wells. Under the assumption of singlet ground-state potential energy surface-dominated photodynamics, the primary photodissociation yields of BrCH2CHO are investigated under both collision-free and collision energy transfer conditions. At atmospheric pressure and under tropospheric actinic flux conditions at ground level, depending on the assumed collisional energy transfer parameter, 150 cm-1 < ⟨ΔEdown⟩ < 450 cm-1, 78-33% of BrCH2CHO undergoes direct photodissociation instead of collisional deactivation at an excitation wavelength of 320 nm. This is significantly higher than the 14% reported for acetaldehyde, hence indicating a strong effect of bromine substitution on the product photolysis yield that is related to additional favorable Br and HBr forming dissociation channels. In contrast to the overall photodissociation quantum yield, the relative branching fractions of the photodissociation products are less dependent on the collisional energy transfer parameter. For a representative value of ⟨ΔEdown⟩ = 300 cm-1 and an excitation wavelength of 320 nm, with 27% for C-C bond fission, 11% for C-Br bond fission, 7% for HBr elimination, and only below 2% each for a consecutive O-Br fission reaction and the photo-tautomerization channel yielding brominated vinyl alcohol, the photodissociation is markedly different from the acetaldehyde case. Finally, as brominated halogenated compounds are of interest for flame inhibition purposes, thermal multichannel unimolecular rate constants were calculated for temperatures in the range from 500 to 2000 K. At a temperature of 2000 K and ambient pressure, the two main reaction channels are the C-Br and C-C bond fissions, contributing 35 and 43% to the total reaction flux, respectively.

We report data that suggest complexes with alkali cations capping the portals of cucurbit[5]uril (CB[5]) bind halide anions size-selectively as observed in the gas phase: Cl- binds inside the CB[5] cavity, Br- is observed both inside and outside, and I- binds weakly outside. This is reflected in sustained off-resonance irradiation collision-induced dissociation (SORI-CID) experiments: all detected Cl- complexes dissociate at higher energies, and Br- complexes exhibit unusual bimodal dissociation behavior, with part of the ion population dissociating at very low energies and the remainder dissociating at significantly higher energies comparable to those observed for Cl-. Decoherence cross sections measured in SF6 using cross-sectional areas by Fourier transform ion cyclotron resonance techniques for [CB[5] + M2X]+ (M = Na, X = Cl or Br) are comparable to or less than that of [CB[5] + Na]+ over a wide energy range, suggesting that Cl- or Br- in these complexes are bound inside the CB[5] cavity. In contrast, [CB[5] + K2Br]+ has a cross section measured about 20% larger than that of [CB[5] + Na]+, suggesting external binding that may correspond with the weakly bound component seen in SORI. While I- complexes with alkali cation caps were not observed, alkaline earth iodides with CB[5] yielded complexes with cross sections 5-10% larger than that of [CB[5] + Na]+, suggesting externally bound iodide. Geometry optimization at the M06-2X/6-31+G* level of ab initio theory suggests that internal anion binding is energetically favored by approximately 50-200 kJ mol-1 over external binding; thus, the externally bound complexes observed experimentally must be due to large energetic barriers hindering the passing of large anions through the CB[5] portal, preventing access to the interior. Calculation of the barriers to anion egress using MMFF//M06-2X/6-31+G* theory supports this idea and suggests that the size-selective binding we observe is due to anion size-dependent differences in the barriers.

We present a strategy of self-nanocavity confinement for substantially boosting the superior electrochemical hydrogen peroxide (H2O2) selectivity for conductive metal-organic framework (MOF) materials. By using operando synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses, the dissociation of key *OOH intermediates during the oxygen reduction reaction (ORR) is effectively suppressed over the self-nanocavity-confined X-Ni MOF (X = F, Cl, Br, or I) catalysts, contributing to a favorable two-electron ORR pathway for highly efficient H2O2 production. As a result, the as-prepared Br-confined Ni MOF catalyst significantly promotes H2O2 selectivity up to 90% in an alkaline solution, evidently outperforming the pristine Ni MOF catalyst (40%). Moreover, a maximal faradic efficiency of 86% with a high cumulative H2O2 yield rate of 596 mmol gcatalyst-1 h-1 for electrochemical H2O2 generation is achieved by the Br-confined Ni MOF catalyst.

Binding of carbon monoxide, CO, and its activation on the surface of the FenCumCO (n + m = 6) clusters are studied in this work. Using the BPW91/6-311 + G(2d) method, we have found that adsorption of the CO molecule on the surface of FenCum (n + m = 6) clusters is thermochemically favorable. Atop and bridge CO cluster coordinations appear for pure, Fe6 and Cu6, and mixed, Fe2Cu4 and Fe4Cu2, clusters. Threefold coordination takes place for Fe3Cu3-CO where the CO bond length, dCO, suffers a largest increase from 1.128 ± 0.014 A for bare CO up to 1.21 A. The CO stretching, νCO, as an indicator for the CO bond weakening is redshifted, from 2099 ± 4 cm-1 for isolated CO up to 1690 cm-1 for Fe3Cu3CO and 1678 cm-1 for Fe6CO. In addition, in Cu6CO, the strongest CO bond is slightly weakened as it has a bond length of 1.15 A and a νCO of 2029 cm-1. There is a correlation between the CO bond weakening and the increase of CO coordination in FenCumCO, which in turns promotes the transference of charges from the metal core into the antibonding orbitals of CO. Substitution of up to three Cu atoms in Fe6 increases the adsorption energies and the activation of CO. Indeed, FenCum (n + m = 6) are promising clusters to catalyze CO dissociation, particularly Fe3Cu3, Fe5Cu, and Fe6, which have large CO bond lengths and CO adsorption energies. The Bader analysis of the electronic density indicates that FenCumCO species with threefold coordination show a rise in the C-O covalent character due to the less electronic polarization. They also show important M → CO charge transfer, which favors the weakening of the CO bond.

Heats of dissolution of crystalline L-glutathione in water and solutions of potassium hydroxide at 298.15 K are measured via direct calorimetry. Numerical values of the standard enthalpies of formation of glutathione in the crystalline state are calculated by additive groups method, based on group systematics with Benson-type classification of fragments that considers the effect of the primary environment on atoms. Standard enthalpies of formation of the tripeptide and the products of its dissociation in aqueous solutions are calculated.

Neon cluster ions Ne$_s^+$ grown in pre-ionized, mass-to-charge selected helium nanodroplets (HNDs) reveal a strong enrichment of the heavy isotope $^{22}$Ne that depends on cluster size s and the experimental conditions. For small sizes the enrichment is much larger than previously reported for bare neon clusters grown in nozzle expansions and subsequently ionized. The enrichment is traced to the massive evaporation of neon atoms in a collision cell that is used to strip helium from the HNDs. We derive a relation between the enrichment of $^{22}$Ne in the cluster ion and its corresponding depletion factor $F$ in the vapor phase. The value thus found for $F$ is in excellent agreement with a theoretical expression that relates isotopic fractionation in two-phase equilibria of atomic gases to the Debye temperature. Furthermore, the difference in zero-point energies between the two isotopes computed from F agrees reasonably well with theoretical studies of neon cluster ions that include nuclear quantum effects in the harmonic approximation. Another fitting parameter provides an estimate for the size s$_i$ of the precursor of the observed Ne$_s^+$. The value is in satisfactory agreement with the size estimated by modeling the growth of Ne$_s^+$, and with lower and upper limits deduced from other experimental data. On the other hand, neon clusters grown in neutral HNDs that are subsequently ionized by electron bombardment exhibit no statistically significant isotope enrichment at all. The finding suggests that the extent of ionization-induced dissociation of clusters embedded in HNDs is considerably smaller than for bare clusters., 14 pages, 5 figures, supplementary material

Two ion populations of protonated Rivaroxaban, [C19H18ClN3O5S + H]+, are separated under pure N2 conditions using differential mobility spectrometry prior to characterization in a hybrid triple quadrupole linear ion trap mass spectrometer. These populations are attributed to bare protonated Rivaroxaban and to a proton-bound Rivaroxaban-ammonia complex, which dissociates prior to mass-selecting the parent ion. Ultraviolet photodissociation (UVPD) and collision-induced dissociation (CID) studies indicate that both protonated Rivaroxaban ion populations are comprised of the computed global minimum prototropic isomer. Two ion populations are also observed when the collision environment is modified with 1.5% (v/v) acetonitrile. In this case, the protonated Rivaroxaban ion populations are produced by the dissociation of the ammonium complex and by the dissociation of a proton-bound Rivaroxaban-acetonitrile complex prior to mass selection. Again, both populations exhibit a similar CID behavior; however, UVPD spectra indicate that the two ion populations are associated with different prototropic isomers. The experimentally acquired spectra are compared with computed spectra and are assigned to two prototropic isomers that exhibit proton sharing between distal oxygen centers.