Temperature Dependence Of Reaction Research Articles

Unveiling gas–liquid metal reactions in metal additive manufacturing: High-fidelity modeling validated with experiments

Gases in the atmosphere inevitably react with the melt pool during metal additive manufacturing (AM). Oxygen is particularly reactive and excessive uncontrolled oxidation is detrimental, so most machines purge the chamber with inert gases, which can minimize but not eliminate such reactions. Alternatively, some users exploit the gas–liquid metal reactivity as an opportunity to introduce beneficial precipitates into the melt pool (“reactive AM”). However, the gas–liquid metal reaction and mechanisms in both scenarios remain unclear. Experimental works hitherto provide different explanations to the same phenomena. Therefore, this work seeks to clarify the mass transfer process of oxygen during metal AM through high-fidelity modeling by considering the competition between diffusion and chemical reaction, suboxide evaporation, and the influence of the vapor plume. The simulation results, validated with experiments, provide consolidated insights into the oxygen evolution behaviour during metal AM. Counterintuitively, higher melt pool temperatures do not necessarily lead to greater oxidation rates during processing. The melt pool has regions of high and low oxygen gains due to temperature-dependent reaction regimes, with concurrent oxygen loss from evaporation of metal suboxides. Thus, the net oxygen flux varies for different materials, and the oxygen content cumulatively changes as multiple tracks are scanned. Overall, this work provides useful guidance to AM community that seek to ameliorate or exploit the inevitable gas–liquid interaction in metal AM. Cost-saving measures may be possible for determining the purity of shielding gas used in AM, and physics-guided measures can be taken to limit or control gas–liquid metal reactions.

Theoretical study of temperature and pressure-dependent rate constants for 8 reactions involving CO and CO2 with C+, C2O2+, CnO3, CnO3+ (n = 1, 2) in carbon dioxide radiolysis

CO2-related reactions and their species play an important role in atmospheric and radiolysis chemistry. However, there remains a lack of temperature and pressure dependent reaction rates for many chemical reactions that are necessary for constructing relevant reaction mechanisms. 8 important atmospheric and radiolysis chemical reactions are investigated theoretically at the rev-DSD/j3z, CCSD/ACCD and CCSD(T)/CBS levels. The temperature, pressure-dependent rate constants are obtained by the RRKM/ME method, which show a reasonable agreement with the reported values. Based on our results, the mechanisms of correlation reaction of CO2 reaction network are refined and provide guidance for studying the directed conversion of CO2.

A Critical View on the Quantification of Model Catalyst Activity

AbstractThe conversion of reactants, reaction rate referred to catalyst mass, and turnover frequency (TOF) are values typically employed to compare the activity of different catalysts. However, experimental parameters have to be chosen carefully when systems of different complexity are compared. In order to characterize UHV-based model systems, we use a highly sensitive sniffer setup which allows us to investigate the catalytic activity by combining three different measurement modes: temperature-programmed desorption, continuous flow, and pulsed-reactivity experiments. In this article, we explore the caveats of quantifying catalytic activity in UHV on the well-studied and highly defined reference system of CO oxidation on Pt(111), which we later compare to the same reaction on Pt19 clusters deposited on Fe3O4(001). We demonstrate that we can apply fast heating ramps for TOF quantification, thus inducing as little sintering as possible in the metastable clusters. By changing the reactant ratio, we find transient reactivity effects that influence the TOF, which should be kept in mind when comparing catalysts. In addition, the TOF also depends on the surface coverage that itself is a function of temperature and pressure. At a constant reactant ratio, in the absence of transient effects, however, the TOF scales linearly with total pressure over the entire measured temperature range from 200 to 700 K since the reaction rate is dependent on both reactant partial pressures with temperature-dependent reaction order. When comparing the maximum TOF at this particular reactant ratio, we find a 1.6 times higher maximum TOF for Pt19/Fe3O4(001) than for Pt(111). In addition, pulsed-reactivity measurements help identify purely reaction-limited regimes and allow for a more detailed investigation of limiting reactants over the whole temperature range.

Exploring Simple Particle-Based Signal Amplification Strategies in a Heterogeneous Sandwich Immunoassay with Optical Detection.

Heterogeneous sandwich immunoassays are widely used for biomarker detection in bioanalysis and medical diagnostics. The high analyte sensitivity of the current "gold standard" enzyme-linked immunosorbent assay (ELISA) originates from the signal-generating enzymatic amplification step, yielding a high number of optically detectable reporter molecules. For future point-of-care testing (POCT) and point-of-need applications, there is an increasing interest in more simple detection strategies that circumvent time-consuming and temperature-dependent enzymatic reactions. A common concept to aim for detection limits comparable to those of enzymatic amplification reactions is the usage of polymer nanoparticles (NP) stained with a large number of chromophores. We explored different simple NP-based signal amplification strategies for heterogeneous sandwich immunoassays that rely on an extraction-triggered release step of different types of optically detectable reporters. Therefore, streptavidin-functionalized polystyrene particles (PSP) are utilized as carriers for (i) the fluorescent dye coumarin 153 (C153) and (ii) hemin (hem) molecules catalyzing the luminol reaction enabling chemiluminescence (CL) detection. Additionally, (iii) NP labeling with hemin-based microperoxidase MP11 was assessed. For each amplification approach, the PSP was first systematically optimized regarding size, loading concentration, and surface chemistry. Then, for an immunoassay for the inflammation marker C-reactive protein (CRP), the analyte sensitivity achievable with optimized PSP systems was compared with the established ELISA concept for photometric and CL detection. Careful optimization led to a limit of detection (LOD) of 0.1 ng/mL for MP11-labeled PSP and CL detection, performing similarly well to a photometric ELISA (0.13 ng/mL), which demonstrates the huge potential of our novel assay concept.

Exploring Energy-Efficient Techniques and Chemical Kinetics in Reactive Nitrogen Species Production with Ambient Air Plasma for Plasma-Activated Water

This study investigates the chemical kinetics of reactive nitrogen species (RNS) formation in plasma-activated water (PAW) using ambient air and evaluates its energy efficiency. A singular plasma/liquid reactor was used, with discharge power varying between 16.4 to 27.0 W and agitation speeds set at 0 and 750 rpm. The reactor operated across temperatures from 5.00 to 35.00 °C during a consistent 180 min plasma activation. Analysis encompassed ionic strength effects, hydronium activity, conductivity, and iodide as a redox indicator for PAW. Findings suggest reactive species predominantly originate in the gas phase and move to the liquid through the gas-liquid interface. HNO3 production in PAW demonstrated a zero-order, temperature-dependent reaction. From activation parameters and ionic strength effects, a determinant step for aqueous HNO3 production was proposed. The influence of discharge power and agitation on HNO3 and HNO2 production was associated with heightened rates due to increased mass transfer and electric field strength. The research highlighted a trade-off between energy efficiency and nitrate production rate, emphasizing an efficiency peak of 72.33 nmol J-1 in PAW, pivotal for cost and operational benefits.

Temperature-dependent microbial reactions by indigenous microbes in bentonite under Fe(III)- and sulfate-reducing conditions

Bentonite is a promising buffer material for constructing spent nuclear fuel (SNF) repositories. However, indigenous microbes in bentonite can be introduced to the repository and subsequent sealing of the repository develops anoxic conditions over time which may stimulate fermentation and anaerobic respiration, possibly affecting bentonite structure and SNF repository stability. Moreover, the microbial activity in the bentonite can be impacted by the heat generated from radionuclides decay. Therefore, to investigate the temperature effect on microbial activities in bentonite, we created microcosms with WRK bentonil (a commercial bentonite) using lactate as the electron donor, and sulfate and/or ferrihydrite (Fe(III)) as electron acceptors with incubation at 18 ℃ and 50 ℃. Indigenous WRK microbes reduced sulfate and Fe(III) at both temperatures but with different rates and extents. Lactate was metabolized to acetate at both temperatures, but only to propionate at 18 ℃ during early-stage microbial fermentation. More Fe(III)-reduction at 18 ℃ but more sulfate-reduction at 50 ℃ was observed. Thermophilic and/or metabolically flexible microbes were involved in both fermentation and Fe(III)/sulfate reduction. Our findings illustrate the necessity of considering the influence of temperature on microbial activities when employing bentonite as an engineered buffer material in construction of SNF repository barriers.

Mixed convective magnetohydrodynamic and thermally radiative flow of reactive couple stress MWCNT–Ag/C2H6O2 hybrid nanofluid in a porous vertical channel: Entropy analysis

This paper is concerned with the analysis of the mixed convective magnetohydrodynamic (MHD) flow of a reactive couple stress multi-walled carbon nanotube −Ag/C2H6O2 hybrid nanofluid in a porous vertical channel subjected to quadratic thermal radiation along with a uniform inclined magnetic field applied to the channel walls. The flow is driven by the pressure gradient force and the buoyancy force, which is modeled based on the nonlinear Boussinesq approximation. The temperature-dependent reaction rate of the reactant molecule is derived using the Arrhenius law. The momentum and energy equations that govern the system are modeled in consideration of slip and convective conditions. The governing equations are non-dimensionalized by applying relevant dimensionless parameters and are solved using the homotopy analysis method (HAM). To analyze the irreversibilities in the system, the entropy generation number and the Bejan number are defined. Different important physical parameters developing in the system are considered for analysis, and their effects are scrutinized on the velocity and temperature profiles along with entropy generation. The emphasis is given to the concentration of nanoparticles along with the parameters arising due to the reactions of the fluid, buoyancy force, inclined magnetic field, thermal radiation, and porous material. The analysis reveals that the velocity and temperature of the fluid lowers with a higher concentration of nanoparticles, radiation parameter, and Hartmann number, whereas develops for the higher slip parameters and inclination of the magnetic field. The entropy generation rate increases with rising slip parameters and depletes for higher nanoparticle concentration, radiation parameter, Hartmann number, and inclination angle. The irreversibility in the system remains dominant due to heat transfer with higher Frank-Kameneskii and activation energy parameters, Hartmann number, and angle of inclination.

Preparation of corn straw-based carbon by “carbonization-KOH activation” two-step method: Gas–solid product characteristics, activation mechanism and hydrogen storage potential

Making excellent carbon-based hydrogen adsorbents requires thoroughly understanding the two-step activation method's reaction mechanism. This research examined the properties of gases and solids with high KOH/biochar ratios (4:1), various carbonization temperatures (400–600 °C), and activation temperatures (700–900 °C). The potential of biochar for hydrogen storage was further examined. These results demonstrate the division of the KOH activation process into four temperature-dependent reaction stages. The emission of CH4, CO, and H2 in various temperature ranges can be significantly influenced by the degree of carbonization and activation temperature. The outcome of activation is primarily determined by the volatile content and reactivity of carbon precursors. Biochar produced at 400 °C for carbonization and 900 °C for activation has a specific surface area (SSA) of 3567.33 m2/g. The oxygen concentration of H-400 decreases as the activation temperature rises, whereas the oxygen-containing structure can be built by raising the carbonization level. The hydrogen storage capacity of biochar was 2.49 wt.% at −196 °C and 1 bar, and increased to 5.51 wt.% at 50 bar, while it is 0.43 wt.% at 50 bar and room temperature. These findings can provide a novel strategy for developing carbon-based hydrogen storage materials.

Cu2CoSnS4 electrocatalyst embedded paper working electrodes for efficient, stable, pH universal, and large-current-density hydrogen evolution reaction

In this study, practical application for the industrial-scale hydrogen evolution reaction (HER) process is established using sustainable Cu2CoSnS4 embedded in paper-working electrodes. The Cu2CoSnS4 is produced using a solvent-free solid-phase approach. The effect of a wide pH range of electrolytes on working electrodes for hydrogen evolution reactions is also investigated. The Cu 2CoSnS4 embedded paper-working electrodes exhibit goodelectrocatalytic activity for hydrogen evolution reaction with low overpotential values of 233, 310, and 261 mV vs RHE at 10 mA/cm 2 in 0.5 M H2SO4,1 M KOH, and 1 M PBS, respectively. These designed electrodes exhibit high double-layer capacitance and electrochemical surface area for a wide pH range. In acidic, alkaline and neutral environments, the catalyst-embedded paper electrodes explicit high turnover frequencies of 2.15 s−1, 2.75 s−1, and 2.11 s−1, respectively. The temperature-dependent hydrogen evolution reaction is studied to calculate the activation energy of the cathodic electrode. Utilising chrono-amperometry for about 118 h in an acidic media, which shows that electrodes have a high degree of stability. In comparison to other previously reported work on catalyst-embedded electrodes, the Cu2CoSnS4 embedded paper-working electrodes offer excellentpotential for HER activity across a wide pH range and are suitable for industrial application.

Experimental and mechanistic study on isothermal oxidative pyrolysis of oil shale

The reasonable introduction of oxygen to the in situ conversion process of oil shale can effectively reduce energy consumption. However, current studies on oxidative pyrolysis often proceed under non-isothermal conditions with sharp fluctuations in temperature which hinders the accurate determination of the reaction process and the corresponding temperature in the system. In this work, we study the isothermal oxidative pyrolysis behavior of two oil shales differing in total organic carbon (TOC) at constant temperatures. The results indicated that with the increase in reaction temperature, low-temperature oxidative pyrolysis (LTOP) and high-temperature oxidative pyrolysis (HTOP) can be distinguished, where the transition temperature is approximately 340 ℃. During the LTOP, kerogen undergoes low-temperature oxidation, including oxygen addition, isomerization, and decomposition reactions. As for the HTOP, high-temperature oxidation coexists with the pyrolysis of kerogen and the subsequent coke oxidation. The pyrolysis reaction gradually dominates the entire reaction with increasing temperature. Accordingly, a temperature-dependent reaction model of oxidative pyrolysis of oil shale in isothermal conditions was validated and the real-time change in the reaction rates was obtained. Also, oil shale with a higher TOC has a more intense reaction and a higher transition temperature of HTOP and LTOP. This work provides a theoretical basis for the further application of oxidative pyrolysis in oil shale exploitation.

Adsorption and surface reactions of C2H2 and C2H4 on Co(0001)

In this paper we have studied adsorption and surface reactions of acetylene and ethylene on Co(0001) in detail by temperature desorption spectrum (TDS), X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). C2H4 adsorption at 130 and 300 K followed by subsequent heating mainly forms C2 clusters and graphitic carbon, respectively, while C2H4 decomposes at 400 and 500 K to form dominant graphitic carbon and carbon adatoms, respectively. C2H2 molecularly adsorbs at 130 K but exclusively dehydrogenates upon heating. The resulting C2H2(a) species at low coverages remains stable up to 400 K and then exclusively dehydrogenates into C2 clusters, while the resulting C2H2(a) species at high coverages remains stable up to 310 K and then majorly dehydrocyclizates into (C2H)n intermediates with ring structures at 340 K which further dehydrogenates into graphitic carbon, and minorly dehydrogenates into C2 clusters. Exposed at 370 K, C2H2 dehydrocyclizates into (C2H)n intermediates with ring structures. These temperature and coverage dependent surface reactions of C2H2 and C2H4 on Co(0001) greatly enrich our fundamental understanding of Co-catalyzed F-T synthesis reaction.

Reactive transport model predicting calcite precipitation: Case of a dynamically operated standing column well

The sanding column well is a promising ground heat exchanger. Nevertheless, hard water can lead to scaling problems. The aim of this study is to calibrate a thermo-hydro-chemical model on experimental data to quantify the factors influencing the scaling. Groundwater samples were collected during 70 days on a standing column well operated jointly with a groundwater treatment unit. A coupled thermo-hydro-chemical model integrating nine aqueous species, calcite mineral reactions, CO2 degassing, and temperature dependent reactions was developed and calibrated on the experimental measurements. Calibration results indicated a precipitated calcite mass of a few nanograms per day. It was observed numerically that when bleed is not active, treating only 2% of the flowrate avoids calcite precipitation. If sealing the wellhead and limiting CO2 degassing are possible, the simulation results indicate a reduction in precipitated calcite masses of 36%.

Exploring non-equilibrium processes and spatio-temporal scaling laws in heated egg yolk using coherent X-rays

The soft-grainy microstructure of cooked egg yolk is the result of a series of out-of-equilibrium processes of its protein-lipid contents; however, it is unclear how egg yolk constituents contribute to these processes to create the desired microstructure. By employing X-ray photon correlation spectroscopy, we investigate the functional contribution of egg yolk constituents: proteins, low-density lipoproteins (LDLs), and yolk-granules to the development of grainy-gel microstructure and microscopic dynamics during cooking. We find that the viscosity of the heated egg yolk is solely determined by the degree of protein gelation, whereas the grainy-gel microstructure is controlled by the extent of LDL aggregation. Overall, protein denaturation-aggregation-gelation and LDL-aggregation follows Arrhenius-type time-temperature superposition (TTS), indicating an identical mechanism with a temperature-dependent reaction rate. However, above 75 °C TTS breaks down and temperature-independent gelation dynamics is observed, demonstrating that the temperature can no longer accelerate certain non-equilibrium processes above a threshold value.

Galactose isomerization to tagatose over MgBr2 follows a temperature-dependent reaction rate kinetics as predicted by first principles-based theories

Tagatose, a classified low-calorie sugar, possesses anti-hyperglycaemic and prebiotic characteristics. Therefore, it is considered a potential food additive supplement (sweetener) for lifestyle health problems in humans. While many reports on its production via biological and chemical methods have been published, the thermodynamic behavior of its synthesis using galactose is rarely focused on. Herein, we report the MgBr2-mediated galactose interconversion to tagatose (single-step) and its kinetic mechanism. The oppositely charged counterions (Mg2+ and Br‒) can induce the reaction via different pathways in a parallel fashion, i.e., the Mg2+ behaving as a Lewis acid can enable via a 1,2-hydride shift pathway, whereas the Br‒ offering the Brønsted basic sites via a proton transfer pathway. This resulted in a tagatose production as high as 22% and 73% selectivity within 60 min at 120 °C in water. Furthermore, the reaction has yielded a single co-product formation (talose up to 7%). From the inverse-gated quantitative NMR analysis, the contribution of the counterions in the reaction is roughly 52%:48% by Mg2+:Br‒. The determination of the temperature-dependent reaction kinetics (elementary steps) was made by employing the first-principles-based theories (i.e., transition state-Eyring theory for the proton transfer pathway that involves no hydride shift and Marcus theory for the hydride shift pathway). The energy calculations of the pathways made via DFT modeling suggested the higher feasibility of a hydride shift mechanism of galactose to tagatose.

TUMME 2023: Tsinghua University Minnesota Master Equation program. New version announcement

This is an updated version of TUMME (Tsinghua University Minnesota Master Equation program), which is a computer program for setting up and solving master equations for chemical kinetics of unimolecular and bimolecular reactions. The master equation is discretized in terms of energy bins, and rate constants are calculated from chemically significant eigenmodes. TUMME has interfaces to Gaussian 16, Polyrate 2023, and MSTor 2023 output files that allow the master equation code to obtain the microcanonical flux coefficients needed for the kernel of the master equation as calculated by conventional transition state theory (TST), variational transition state theory (VTST) with various tunneling methods, or multi-structural or multi-path VTST (MS-VTST or MP-VTST) with various tunneling methods. The tunneling methods supported include zero-curvature tunneling (ZCT), small-curvature tunneling (SCT), large-curvature tunneling (LCT), and microcanonically optimized multidimensional tunneling (μOMT). For mechanisms involving only unimolecular isomerization (no bimolecular pairs), TUMME can set up and solve a conservative master equation for both rate constants and time-dependent energy-bin populations. For mechanisms involving bimolecular pairs, TUMME 2023 can set up and solve two kinds of master equation: (i) a nonconservative master equation for calculating rate constants of bimolecular reactions and (ii) a conservative master equation that includes bimolecular association in the transition matrix and that can be used for calculating the time evolution of the concentration of a pseudo-first-order bimolecular reactant. TUMME is written in double precision with Python 3; quadruple and octuple precision are also available for some subtasks in C++. The Python code can run in serial or parallel (MP or MPI), and C++ code can run on a single processor or on multiple processors with OpenMP. The program includes a manual and a tutorial. New version program summaryProgram Title: TUMME 2023CPC Library link to program files:https://doi.org/10.17632/whcnvm2mc9.2Developer's repository link:https://doi.org/10.5281/zenodo.7943283Licensing Provisions: Apache-2.0 for the program and CC-BY-4.0 for the manualProgramming languages: Python 3 and C++Does the new version supersede the previous version?: YesJournal reference of previous version: Comput. Phys. Commun. 270 (2022) 108140 [1]External libraries: Numpy, Scipy, Numba, mpi4py (optional), modified mpack (optional), qd (optional), omp (optional)Interfaces to other programs: Gaussian 16 [2], Polyrate 2023 [3], and/or MSTor 2023 [4]Nature of problem: Characterize and calculate rate constants for a temperature-dependent and pressure-dependent complex reaction systemSolution method: Solve the energy-grained master equation based on the chemically significant eigenmodes to get phenomenological rate constants and time evolutions of the populations [1,5–7].Reason for new version: The new version increases the functionality and accuracy, and it offers an easier way to run the program. In addition, some bugs have been corrected.Summary of revisions:1.Added an option (available in high precision) to treat pseudo-first-order bimolecular reactions to obtain the time evolution of the reactants and intermediates. [8]2.Added an inverse-Laplace-transform option in the REACTION block.3.Abandoned rounding the sizes of energy bins to an integer wavenumber (ESOT).4.Changed the way to run TUMME by providing an executable bash script.5.Slightly adjusted the strategy for eigenmode mergers to deal with some unexpected cases.6.Adjusted the output for the partition functions.7.Added options for large-curvature tunneling (LCT) and microcanonically optimized multidimensional tunneling (μOMT).8.Added the keyword pyrfile to support a Polyrate 2023 [3] file that ends with a suffix .fu100.9.Fixed some bugs.10.Updated the manual and added a tutorial to the program distribution, so the distribution now has both a manual and a tutorial.

Trivinylphosphine Oxide: Synthesis, Characterization, and Polymerization Reactivity Investigated Using Single-Crystal Analysis and Density Functional Theory.

Organophosphorus chemicals are versatile and important in industry. Trivinylphosphine oxide (TVPO), for example, exhibited a promising precursor as a flame-retardant additive for industrial applications. Density functional theory (DFT) simulations were used to explore the kinetic and thermodynamic chemical processes underlying the nucleophilic addition reactions of TVPO in order to better understand their polymerization mechanisms. An experimental X-ray single-crystal study of TVPO supported this work's theory based on its computed findings. TVPO was prepared using POCl3 and VMB in a temperature-dependent reaction. TVPO, the thermodynamically favourable product, is preferentially produced at low temperatures. The endothermic anionic addition polymerization reaction between TVPO and VMB begins when the reaction temperature rises. An implicit solvation model simulated TVPO and piperazine reactions in water, whereas a hybrid model modelled VMB interactions in tetrahydrofuran. The simulations showed a pseudo-Michael addition reaction mechanism with a four-membered ring transition state. The Michael addition reaction is analogous to this process.

Determination of the Corrosion–Oxidation Turning Point at the Field’s Metal/Chromium Interface by Electrical Contact Resistance Measurement

The correlation of the electrical contact resistance measurement and microanalysis of the Field’s metal (FM)/Cr interface was used to determine the temperature-dependent reactions at the interface. Oxidation of Cr by oxygen contained in FM was identified through a sharp increase of the contact resistance around a certain temperature, above which the following resistance decrease was associated to a corrosion process. The corrosion–oxidation turning point was observed around 390 ± 1.7 °C. Cr saturation in FM combined with complete consumption of the oxygen contained in the FM induced a stabilization of the interface giving a specific contact resistance of about 30 µΩ·cm2.

Diffusive mass transfer and protein removal in the alkaline cleaning of a jellylike whey protein fouling layer

AbstractSingle steps in cleaning a fouled heat exchanger surface eventually determine the cleaning kinetic and thus the overall performance of a cleaning process. Up to date the complex mechanisms of the mutual supportive processes in cleaning are not yet fully understood. This contribution presents a stepwise approach to investigate the individual process steps starting with the diffusion of the cleaning agent NaOH into a WPI gel, studied at stationary and flow conditions. In the experiments, temperature affected both the diffusion step and the subsequent removal but to different extents. This was further specified and it was found that there is an induction time for the release of disengaged proteins, accounting for the speed of the temperature dependent degrading reactions.

Cold CAS ion trap – 22 pole trap with ring electrodes for astrochemistry

The enhancement of a cryogenic radio frequency 22 pole trap instrument by the addition of ring electrodes is presented in detail. The ring electrodes tightly surround the poles and only a fraction of the applied electric potential penetrates to the trap axis, facilitating the fine control of slow cold ions. A precise computational model, describing the effective mechanical potential created by the applied static and rf fields, governing the ion behaviour, is employed to demonstrate and understand the operation of our setup. The use of ring electrodes for improved extraction of cold stored ions is shown. Variable trapping potentials, placed on one ring electrode, can be used to control the evaporation of only those H + ions from the trap, whose kinetic energy exceeds the barrier. This ring electrode trapping opens new possibilities to study processes of minimal kinetic energy release, e. g. spin exchange. We propose a robust modified method for the determination of temperature dependent ion molecule reaction rates, resistant to effects caused by neutral gas freezing and demonstrate it on the reaction of CO + / CO 2 + with H 2 / D 2 . Finally, the use of a supercontinuum laser for quick localisation of spectroscopic bands is examined on the N 2 + Meinel system.

Quantum Tunneling in Peroxide O-O Bond Breaking Reaction.

The importance of quantum-mechanical tunneling becomes increasingly recognized in chemical reactions involving hydrogen as well as heavier atoms. Here we report concerted heavy-atom tunneling in an oxygen-oxygen bond breaking reaction from cyclic beryllium peroxide to linear dioxide in cryogenic Ne matrix, as evidenced by subtle temperature-dependent reaction kinetics and unusually large kinetic isotope effects. Furthermore, we demonstrate that the tunneling rate can be tuned through noble gas atom coordination on the electrophilic beryllium center of Be(O2), as the half-life dramatically increased from 0.1 h for NeBe(O2) at 3 K to 12.8 h for ArBe(O2). Quantum chemistry and instanton theory calculations reveal that noble gas coordination notably stabilizes the reactants and transition states, increases the barrier heights and widths, and consequently reduces the reaction rate drastically. The calculated rates and in particular kinetic isotope effects are in good agreement with experiment.