Importance of Spin Channels from Radical-Radical Reactions in Hydrogen-Oxygen Combustion Mechanisms at High Temperatures.

Radical-radical reactions can generate two channels with high and low spins. In this work, ten radical-radical reactions with different spin channels and four radical-molecule reactions in hydrogen-oxygen combustion were systematically investigated from a theoretical perspective. The potential energy surface (PES) of radical-radical reactions reveals that the high- and low-spin states of the reactant are energetically degenerate and the two channels are energetically feasible. The difference in rate constants between the high- and low-spin channels gradually decreases as the temperature increases. Then, the kinetic parameters of the 14 bimolecular reactions in the hydrogen-oxygen mechanism of the University of California, San Diego (UCSD), were replaced to simulate the ignition delay time and laminar flame speed. The simulation results agree well with the available experimental findings, indicating the necessity of considering both high- and low-spin channels for kinetic simulation.

Theoretical Study of the Temperature- and Pressure-Dependent Rate Constants for Nine Reactions between COn (n = 0-4), Om (m = 1-3), C2O, and C3O2 during the Radiolysis of Carbon Dioxide.

We investigate the reaction pathways of nine important CO2-related reactions using the revDSD-PBEP86-D3(BJ)/jun-cc-pV(T+d)Z level and simultaneously employ an accurate composite method (jun-Cheap) based on coupled-cluster (CC) theory. Subsequently, the Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is solved to calculate the temperature- and pressure-dependent rate constants. This work investigates reactions involving transition states that have been overlooked in previous literature, including the dissociation of singlet-state C3O2, the triple channel formation of C2O + CO to form C3O2, and the formation of O3 + CO. The results show that CO3 is highly prone to dissociation at high temperatures. Finally, the kinetic data show that over a wide temperature range, our calculations are consistent with previous experimental measurements. The majority of the reaction rate constants studied exhibit significant pressure dependence, while the O3 + CO reaction is pressure-independent at low temperatures. These results are instrumental in the development of detailed kinetic models for the CO2 radiolysis reaction network.

Molecular Dynamics Simulation of Thermal Nonequilibrium and Chemical Reaction Processes in Hydrogen Combustion.

Using reactive force field (ReaxFF) and molecular dynamics simulation, we investigate the combustion process of hydrogen-oxygen systems in initial thermal nonequilibrium states with different translational and rovibrational temperatures for oxygen. The system studied in this work contains 300 oxygen molecules and 700 hydrogen molecules with a density of 7 times the air density. For this system, the characteristic relaxation times of oxygen and hydrogen vibrational energies are 0.173 and 0.249 ns, respectively. 0.6% of hydrogen undergoes a chemical reaction with oxygen during the thermal nonequilibrium relaxation stage. For the distribution of translational energy and vibrational energy of oxygen in the thermal nonequilibrium state, the maximum mean error of the statistical distribution in the simulation and the Boltzmann distribution at temperature calculated from the average kinetic energy of molecules is about 2.25 × 10-5. At the same time, it was observed in the simulation that many-body interactions play a certain role in the combustion process. Furthermore, we compare the ignition time and temperature rise behavior of different combustion mechanisms and molecular dynamics simulations starting from the thermal equilibrium state. These results will provide meaningful references for the construction of thermal nonequilibrium combustion chemical reaction mechanisms.

A Method Probing High-Temperature Oxidation Behavior of Crystalline Materials.

To date, the oxidation behavior of crystal materials is not fully understood; additional research is needed to understand the oxidation of materials. Herein, density functional theory (DFT) calculations and a 3D kinetic Monte Carlo (KMC) model are used to investigate the infiltration and diffusion behaviors of oxygen atoms within the crystal. Oxygen molecules readily adsorbes on crystal surfaces of the material and rapidly dissociates, verified by both first-principles calculations and energy-dispersive spectrometer (EDS) results. The infiltration ability of oxygen atoms into the inner crystal layers is affected by the surrounding oxygen atom, lattice compactness, and other factors. Energy-barrier calculations show that crystal thin/dense layers have significant effects on the crystal oxidation process, so high-pressure technology is used to investigate this correlation experimentally. KMC calculations and thermogravimetric analyses (TGA) show the infiltration behavior of oxygen atoms in the main crystal plane (211) toward the inner layers has the highest proportion to the actual high-temperature oxidation behavior of the title material. The results of both the KMC calculations and thermal experiments show the material peeled off upon further oxidation, which accelerates oxidation. At the same time, high-pressure treatment increases the oxidation resistance of materials at lower temperatures (<600 °C).

Transport Parameters for Combustion Species Based on cAMOEBA Polarizable Force Field.

In this study, we report a simplified yet accurate general AMOEBA polarizable force field for combustion-interested molecular species, denoted as Combustion-AMOEBA or cAMOEBA. By eliminating the permanent atomic dipoles and quadrupoles, retaining the explicit polarization and defining the general atom types of each molecule species, including alkanes, alkenes, alkynes, alcohols, peroxides, and aldehydes, a simplified and general cAMOEBA force field was constructed and validated using the benchmark results obtained at the QCISD(T)/CBS level of theory. In this way, the tedious parametrization step for permanent atomic multipoles of each new molecule in the original AMOEBA (Poltype/MP2) force field could be avoided, hence providing the capability of accurate high-throughput calculation for a large number of molecules at lower computational cost. The averaged difference between the calculated transport parameters, σ and ε, for approximately 100 different molecules and four bath gases (He, Ne, Ar, and N2) using cAMOEBA and AMOEBA (Poltype/MP2) are of 0.09% and 1.27%, respectively, showing a good consistence of the general cAMOEBA force field with the original AMOEBA (Poltype/MP2) force field where the multipole force field parameters were obtained from quantum mechanical calculation for each small molecule. Our results also indicated that the Lorentz-Berthelot combination rule was more applicable than Waldman-Hagler for obtaining the molecular Lennard-Jones parameters of pure gases from one bath gas, while the Waldman-Hagler combination rule was better for obtaining such parameters from all four bath gases. The pure gas parameters obtained using cAMOEBA can be applied to develop high quality transport property database for combustion modeling.

General Charge Transfer Dipole Model for AMOEBA-Like Force Fields.

The development of highly accurate force fields is always an importance aspect in molecular modeling. In this work, we introduce a general damping-based charge transfer dipole (D-CTD) model to describe the charge transfer energy and the corresponding charge flow for H, C, N, O, P, S, F, Cl, and Br elements in common bio-organic systems. Then, two effective schemes to evaluate the charge flow from the corresponding induced dipole moment between the interacting molecules were also proposed and discussed. The potential applicability of the D-CTD model in ion-containing systems was also demonstrated in a series of ion-water complexes including Li+, Na+, K+, Mg2+, Ca2+, Fe2+, Zn2+, Pt2+, F-, Cl-, Br-, and I- ions. In general, the D-CTD model demonstrated good accuracy and good transferability in both charge transfer energy and the corresponding charge flow for a wide range of model systems. By distinguishing the intermolecular charge redistribution (charge transfer) under the influence of an external electric field from the accompanying intramolecular charge redistribution (polarization), the D-CTD model is theoretically consistent with current induced dipole-based polarizable dipole models and hence can be easily implemented and parameterized. Along with our previous work in charge penetration-corrected electrostatics, a bottom-up approach constructed water model was also proposed and demonstrated. The structure-maker and structure-breaker roles of cations and anions were also correctly reproduced using Na+, K+, Cl-, and I- ions in the new water model, respectively. This work demonstrates a cost-effective approach to describe the charge transfer phenomena. The water and ion models also show the feasibility of a modulated development approach for future force fields.

Pyroligneous acids from biomass charcoal by-product as a potential non-selective bioherbicide for organic farming: its chemical components, greenhouse phytotoxicity and field efficacy.

Effective and environmentally friendly herbicides are urgently needed to meet consumer demand for organic products. To evaluate the weed control effect of four pyroligneous acid (PAs) mixtures, the byproducts of bamboo/wood/straw vinegar, two herbicide discovery tests were done: (1) the greenhouse tests by using four indicative plants: wheat (Triticum sativa), radish (Raphanus sativus), cucumber (Cucumus sativus), and Echinochloa crusgalli (L.) Beauv; (2) Field trials with four weeds: E. crusgalli, Eleusine indica (L.) Gaertn, Alternanthera philoxeroides (Mart.) Griseb, and Conyza canadensis (L.) Cronq. Greenhouse tests showed that the efficacy of PAs and acetic acid (AA) to control four test plants increased with the increasing of PAs concentration. The inhibition rates of four tested PAs (FBV (0.6-9.2% AA + (0.3-5.0% tar), HWV (0.2-1.8% AA + 0.3-4.3% tar), ASV (0.5-8.7% AA + 0.4-7.0% tar), and CWV (0.7-5.3% AA + 0.5-7.5% tar) gave inhibition rates of 56 ± 4-97 ± 2%, 21 ± 2-90 ± 6%, 29 ± 3-98 ± 5%, and 44 ± 6-86 ± 2%, respectively, and the field effects of PAs against four weeds were enhanced with the increasing of concentrations and time after spraying (1 to 14 days). Their control effects against E. crusgalli, E. indica, A. philoxeroides, and C. canadensis were 4 ± 1-93 ± 4%, 7 ± 3-90 ± 3%, 32 ± 2-95 ± 3%, and 31 ± 5-96 ± 4%, respectively. The mixed effect of the four PAs was higher than the same dose of AA. These results will help to determine the potential of PAs to be developed as non-selective herbicides to control weeds in organic farming.

Effect of (H2O) n (n = 0-3, 13) on the NH3 + OH reaction in the gas and liquid phases.

We studied the effect of water clusters on the NH3 + OH reaction at both the DFT and CCSD(T) levels. The calculated rate constants for the pure reaction are 2.07 × 10-13 and 1.35 × 10-13 cm3 molecule-1 s-1 in the gas and liquid phases, respectively, and the gas-phase rate constants are consistent with the corresponding experimental result (1.70 × 10-13 cm3 molecule-1 s-1), while the liquid-phase rate constants are slightly smaller than the experimental value (5.84 × 10-12 cm3 molecule-1 s-1). In the gas phase, the presence of (H2O) n (n = 1-3) decreases the rate constant compared to the pure NH3 + OH reaction, and these results are in agreement with many reported H2O-catalyzed reactions. For the liquid phase reaction, compared with the case of n = 0-3, when the size of the water molecule cluster surrounding the OH radical is n = 13, the rate constant of the title reaction increases. Our study also shows that proton transfer is also a factor which accelerates the liquid phase NH3 + OH reaction.

Full-dimensional quantum mechanical calculations for the tunneling behavior of HOCO dissociation to H + CO2.

The tunneling behavior during HOCO dissociation to H + CO2 was investigated by full-dimensional quantum mechanical calculations based on an accurate global potential energy surface. The tunneling lifetimes for the low-lying 1500 vibrational states were calculated using the low-storage filter diagonalization method after a 1 million-step Chebyshev propagation. In the calculated energy range, the lifetimes of different vibrational states with similar energy are found to differ by 3-4 orders of magnitude, and the lower limit for these tunneling lifetimes is consistent with the experimental results reported by Continetti et al. For the given vibrational progressions, the lifetime of the vibrational states decreases with the increasing energy level, which is consistent with the results of 1D simulation calculations reported by Bowman, but the declining curve obviously fluctuates, and the declining slope is significantly different from that obtained by 1D simulation. Due to a difference in the effective barrier width, the mode-specific behavior of the tunneling effect is manifested in that the O-C-O' and H-O-C bend modes lead to the largest enhancement and an inhibitory effect on the tunneling process, respectively.

High-Polarity Fluoroalkyl Ether Electrolyte Enables Solvation-Free Li+ Transfer for High-Rate Lithium Metal Batteries.

Lithium metal batteries (LMBs) have aroused extensive interest in the field of energy storage owing to the ultrahigh anode capacity. However, strong solvation of Li+ and slow interfacial ion transfer associated with conventional electrolytes limit their long-cycle and high-rate capabilities. Herein an electrolyte system based on fluoroalkyl ether 2,2,2-trifluoroethyl-1,1,2,3,3,3-hexafluoropropyl ether (THE) and ether electrolytes is designed to effectively upgrade the long-cycle and high-rate performances of LMBs. THE owns large adsorption energy with ether-based solvents, thus reducing Li+ interaction and solvation in ether electrolytes. With THE rich in fluoroalkyl groups adjacent to oxygen atoms, the electrolyte owns ultrahigh polarity, enabling solvation-free Li+ transfer with a substantially decreased energy barrier and ten times enhancement in Li+ transference at the electrolyte/anode interface. In addition, the uniform adsorption of fluorine-rich THE on the anode and subsequent LiF formation suppress dendrite formation and stabilize the solid electrolyte interphase layer. With the electrolyte, the lithium metal battery with a LiFePO4 cathode delivers unprecedented cyclic performances with only 0.0012% capacity loss per cycle over 5000 cycles at 10 C. Such enhancement is consistently observed for LMBs with other mainstream electrodes including LiCoO2 and LiNi0.5 Mn0.3 Co0.2 O2 , suggesting the generality of the electrolyte design for battery applications.

Calculation of Transport Parameters Using ab initio and AMOEBA Polarizable Force Field Methods.

The transport properties of chemical species such as coefficients of diffusion, thermal conductivity, and viscosity have been widely used in combustion modeling. Lennard-Jones parameters fitted from the accurate intermolecular potential energy surfaces are crucial to obtain such information. Hence, a fast and accurate energy function is always desired for this purpose. In this study, the quality of a widely used polarizable force field AMOEBA was examined for the interaction between noble gases and n-alkanes. First, the intermolecular energy was compared between AMOEBA, MP2/CBS, MP2/aug'-cc-pVDZ, and QCISD(T)/CBS. The root mean squared error of the original AMOEBA was 10.31 cm-1 against QCISD(T)/CBS for all conformations. This was comparable with the errors of 10.84 and 7.75 cm-1 for MP2/aug'-cc-pVDZ and MP2/CBS, respectively. Further optimizing the van der Waals parameters of noble gases, the error of the force field against QCISD(T)/CBS was reduced to 6.24 cm-1, even better than the MP2/CBS results. Based on the optimized force field parameters, the intermolecular Lennard-Jones parameters were derived using the spherically averaged method and one-dimensional minimization method for a set of (n-alkanes, noble gases) pairs. The discrepancy of the one-dimensional minimization predicted Lennard-Jones collision rates from the tabulated values was typically within 10%, while it could be as large as 20-30% for the spherically averaged method. Additionally, the binary diffusion coefficients were calculated using the present Lennard-Jones parameters. In this case, the parameters derived from the spherically averaged method perform better. The mean unsigned error of the diffusion coefficients is usually within 5%, which is in good agreement with the experimental results. The results demonstrate that the AMOEBA force field can be used to generate the transport parameters systematically.

Microwave Hotspots: Thermal Nonequilibrium Dynamics from the Perspective of Quantum States.

The observed microwave effects include thermal effect, superheating or hotspots, and selective heating. These phenomena are almost impossible in classical heating, and the existence of nonthermal effect is still a controversial topic. Hotspot effect is a phenomenon that is often observed in microwave-assisted reaction and is significantly different from the traditional heating reaction. We use the quantum-state specified master equation model of microwave-assisted reaction proposed in 2016 to study the possible mechanism of microwave hotspots. We divide the hotspots into space hotspots and intramolecular hotspots, which correspond to thermal conduction and luminous behavior, respectively. For the model system in the microwave field, the microwave hotspot cannot be generated at a very low temperature of 100 K, and it is possible to generate the microwave hotspot above 300 K. Moreover, the probability of generating the microwave hotspot at 500 K is about 75 times higher than that at 350 K. The appearance of this nonlinear phenomenon is related to the uneven distribution of temperature and microwave intensity in the macroscopic level and directly related to the nonequilibrium behavior caused by microwave absorption in the quantum-state level. It is suggested that microwave hotspots can be induced by heating the given regions in the reaction vessel in advance. In addition, the formation of intramolecular hotspots can also be induced by pre-exciting the local groups in specific molecules.

Bamboo Tar as a Novel Fungicide: Its Chemical Components, Laboratory Evaluation, and Field Efficacy Against False Smut and Sheath Blight of Rice and Powdery Mildew and Fusarium Wilt of Cucumber.

The application of agricultural and forest residues can benefit the environment and the economy; however, they also generate a large amount of byproducts. In this study, bamboo tar (BT), a waste product of bamboo charcoal production, was dissolved in natural ethanol and the surfactant alkyl glucoside to manufacture a 50% (wt/wt) BT emulsifiable concentrate (BTEC) biopesticide. BTEC was screened for fungicidal activity against pathogens. The greatest activity was seen against Ustilaginoidea virens with a half-maximal effective concentration (EC50) value of 6 mg/liter. Four phytopathogenic fungi, Podosphaera xanthii, Rhizoctonia solani, Fusarium oxysporum, and Botrytis cinerea, showed EC50 values of <60 mg/liter. Greenhouse tests in vivo showed 2,000 mg/liter BTEC had a 78.4% protective effect against U. virens, and replicated treatments had an 80.6% protective effect. In addition, replicated 2-year field trials were conducted in two geographic locations with four plant diseases: false smut (U. virens), rice sheath blight (Thanatephorus cucumeris [Frank] Donk), cucumber powdery mildew (P. xanthii), and cucumber Fusarium wilt (F. oxysporum). Results showed that 1,000 to 2,000 mg/liter BTEC significantly inhibited these diseases. Gas chromatography-mass spectrometry analysis showed that the total phenolic mass fractions of two BT samples were 45.39 and 48.26%. Eleven components were detected, and their percentage content was as follows (from high to low): 2,6-dimethoxyphenol > 2- or 4-ethylphenol > 2- or 4-methylphenol > phenol > 4-ethylguaiacol > dimethoxyphenol > 4-methylguaiacol > 4-propenyl-2,6-dimethoxyphenol > 2,4-dimethylphenol. Some of the phenolic compounds identified from the tar might be fungicidally active components. BT is a biochar waste, which has potential as a biofungicide and has promise in organic agriculture. The value of this tar may not be because of any fundamental physical differences from other synthetic fungicides but rather caused by reduced production expenses and more efficient use of waste products.

Influence of high-dose continuous applications of pyroligneous acids on soil health assessed based on pH, moisture content and three hydrolases.

Pyroligneous acids can be used in herbicides, but the dosage used often more than 1000 kg ha-1. Five treatments including the application of bamboo, wood, straw vinegar, acetic acid and sulphuric acid at high dosages sprayed once every 6 days, for a total of 3 times. We then continuously monitored the changes in soil pH, moisture content and the activities of three soil hydrolase enzymes involving in urease, protease and sucrase. We found that after 1~3 days of spraying with all 5 kinds of acid, the soil pH was not immediately reduced, but from 3 days after application onward it was reduced by a maximum of 1.54~1.75, which showed that the soil had some buffering capacity. Over time, the pH began to return to the water control pH value, which showed that the soil also had good restorative capacity. After the second and third times of spraying, the pH change measured showed no cumulative effect, which demonstrated that the soil had adaptive capacity. We accidentally found that bamboo vinegar could improve the soil pH by a maximum of 0.65~1.02, while the other four acids reduced its pH. Bamboo vinegar was found to contain the 6 compounds while wood and straw vinegar contained none of these compounds. These compounds may be a new potential reagent(s) for improving the pH. Three soil sample processing methods tested for determining pH, including the moist soil test, oven-dry soil test and air-dried soil test, all produced extremely and significantly different pH values. Five acids were unable to significantly improve the water holding capacity of the soil; they had adverse effects on the activity of the urease enzymes while beneficial effects on the protease and sucrase enzymes. Therefore, pyroligneous acid and acetic acid have no effects on soil health as herbicides.

First-principles study of the adsorption behaviors of Li atoms and LiF on the CF x (x = 1.0, 0.9, 0.8, 0.5, ∼0.0) surface.

Based on first principles calculation, the adsorption properties of Li atoms and LiF molecules on the fluorographene (CF x ) surface with different F/C ratios (x = 1.0, 0.9, 0.8, 0.5 and ∼0.0) have been studied in the present work. The calculated binding energy of Li and CF x is greater than 2.29 eV under different F/C ratios, indicating that the battery has the potential to maintain a high discharge platform during the whole discharge process. But the adsorption energies of LiF on a CF x layer for different F/C ratios are 0.12-1.04 eV, which means LiF is not easy to desorb from a CF x surface even at room temperature. It will stay on the surface for a long time and affect the subsequent discharge. Current calculations also show the structure of the CF x -skeleton will change greatly during the reaction, when there are many unsaturated carbon atoms on the CF x surface, such as at x = 0.8 and 0.5. Moreover, the discharge voltage is strongly dependent on the discharge site. After discharge, the CF x -skeleton may continue to relax and release a lot of heat energy.

New Insight on Hydrogen Evolution Reaction Activity of MoP2 from Theoretical Perspective.

We systematically investigated the hydrogen evolution reaction (HER) of six facets of MoP2 based on the periodic density functional theory (DFT). The calculated values of Gibbs free energy of hydrogen adsorption (ΔGH) indicated that the (111) facet has a good HER activity for a large range of hydrogen coverages. The zigzagged patterns before 75% hydrogen coverage suggest a facilitation among Mo1, P1 and Mo2 sites, which are attributed to repeat occupancy sites of H atoms. From ab initial atomistic thermodynamics analysis of hydrogen coverage, we gained that the most stable coverage of hydrogen is 18.75% at 1 atm H2 and 298 K. Finally, the doping effects on HER activity were investigated and found that catalytic performance can be improved by substituting P with an S or N atom, as well as substituting the Mo atom with an Fe atom, respectively. We hope this work can provide new insights on further understanding of HER for MoP2 and give instructions for the experimental design and synthesis of transition metal phosphides (TMPs)-based high-performance catalysts.

Absorption Spectra of Acetylene, Vinylidene, and Their Deuterated Isotopologues on Ab Initio Potential Energy and Dipole Moment Surfaces.

The absorption spectra of acetylene (HCCH) and vinylidene (H2CC) as well as their deuterated isotopologues are investigated theoretically on a near spectroscopically accurate full-dimensional potential energy surface reported in an earlier publication, using dipole moment surfaces reported in this work, which are constructed with a neural network method from a large number of ab initio data points. These global surfaces cover not only the deep acetylene well but also the vinylidene well, as well as the transition region between the two isomers. The agreement with available experimental data for acetylene is excellent, validating both the potential energy surface and the dipole moment surfaces. The infrared spectra of vinylidene and its deuterated isotopologues are predicted. The potential and dipole moment surfaces lay the foundation for future spectroscopic studies of the acetylene-vinylidene isomerization involving large-amplitude motions.

Quantum dynamical investigation of product state distributions of the F + CH3OH → HF + CH3O reaction via photodetachment of the F-(HOCH3) anion.

The photodetachment of the F-(HOCH3) anion, which sheds light on the post-transition-state dynamics of the F + CH3OH → HF + CH3O reaction, is investigated using a reduced-dimensional quantum wave packet method on ab initio based potential energy surfaces for both the neutral and anionic species. The detachment of an electron in the anion precursor produces both bound and resonance species in a hydrogen-bonded potential well in the product channel, in qualitative agreement with the photoelectron-photofragment coincidence (PPC) spectrum. The measured photoelectron-photofragment coincidence spectroscopy is reproduced by the quantum calculations. Our results indicated that the HF product is vibrationally excited, while the OCH3 product is internally cold, thus providing unambiguous assignments of the experimental spectrum.

Hydrogen evolution reaction activity related to the facet-dependent electrocatalytic performance of NiCoP from first principles.

Transition metal phosphides (TMPs) have been proven to act as highly active catalysts for the hydrogen evolution reaction (HER). Recently, single-phase ternary NiCoP electrocatalysts have been shown through experiments to display remarkable catalytic activity for the HER during water splitting. But, the inherent mechanism is not well understood. Herein, the HER activity of NiCoP with low-Miller-index facets, including (111), (100), (001)-NiP-t, and (001)-CoP-t, was systematically investigated using periodic density functional theory (DFT). The calculated Gibbs free energy of hydrogen adsorption (ΔG H) values reveal that all calculated facets have good catalytic activity for the HER. The (111) facet with the lowest surface energy in a vacuum has optimal ΔG H values close-to-zero for a range of hydrogen coverage. Ab initio thermodynamic analysis of hydrogen coverage was conducted to obtain the stabilities of surfaces, which follow the trend: (111) > (001)-CoP-t > (100) > (001)-NiP-t at 1 atm H2 and 298 K. We hope that this work can shed new light on further understanding the HER in relation to NiCoP and can give guidance for the design and synthesis of transition bimetal phosphide-based catalysts.

Activation of Reactions in the Complex Region Using Microwave Irradiation.

Many mode-specific behaviors in the gas phase and at the gas-surface interface have been reported in the past decades. Infrared activation of a reagent vibrational mode is often used to study these reactions. In this work, an inexpensive and easily applied scheme using microwave irradiation is proposed for activating complex-forming reactions by transferring populations between closely spaced resonances. The important combustion reaction of H + O2 ↔ O + OH is used as a model system to demonstrate the feasibility of the proposed approach. The existence of a nonzero transition dipole moment matrix element between two highly excited resonance states separated by a small energy gap in the model system may allow one to use microwave irradiation to intervene and control the model reaction. The high energy resonance states of the model reaction can also release their energy by photon emission, which is in agreement with the experimentally observed chemiluminescence process.