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.

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.

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).

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.

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.

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.

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.

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.

Full-dimensional quantum mechanics calculations for the spectroscopic characterization of the isomerization transition states of HOCO/DOCO systems.

Full-dimensional quantum mechanics calculations were performed to determine the vibrational energy levels of HOCO and DOCO based on an accurate potential energy surface. Almost all of the vibrational energy levels up to 3500 cm-1 from the vibrational ground state were assigned, and the calculated energy levels in this work are well in agreement with the reported results by Bowman. The corresponding full dimensional wavefunctions present some special features. When the energy level approaches the barrier height, the trans-HOCO and cis-HOCO states strongly couple through tunneling interactions, and the tunneling interaction and Fermi resonance were observed in the DOCO system. The energy level patterns of trans-HOCO, cis-HOCO and trans-DOCO provide a reasonable fitted barrier height using the fitting formula of Field et al., however, a discrepancy exists for the cis-DOCO species which is considered as a random event. Our full-dimensional calculations give positive evidence for the accuracy of the spectroscopic characterization model of the isomerization transition state reported by Field et al., which was developed from one-dimensional model systems. Furthermore, the special case of cis-DOCO in this work means that the isotopic substitution can solve the problem of the accidental failure of Field's spectroscopic characterization model.

Classical Trajectory Study of Collision Energy Transfer between Ne and C2H2 on a Full Dimensional Accurate Potential Energy Surface.

Collision energy transfer plays an important role in gas phase reaction kinetics and relaxation of excited molecules. However, empirical treatments are generally adopted for the collisional energy transfer in the master equation based approach. In this work, classical trajectory approach is employed to investigate the collision energy transfer dynamics in the C2H2-Ne system. The entire potential energy surface is described as the sum of the C2H2 potential and interaction potential between C2H2 and Ne. It is highlighted that both parts of the entire potential are highly accurate. In particular, the interaction potential is fit to ∼41 300 configurations determined at the level of CCSD(T)-F12a/cc-pCVTZ-F12 with the counterpoise correction. Collision energy transfer dynamics are then carried out on this benchmark potential and the widely used Lennard-Jones and Buckingham interaction potentials. Energy transfers and related probability densities at different collisional energies are reported and discussed.

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.

Nonadiabatic Tunneling in Photodissociation of Phenol.

Using recently developed full-dimensional coupled quasi-diabatic ab initio potential energy surfaces including four electronic ((1)ππ, (1)ππ*, 1(1)πσ*, and 2(1)πσ*) states, the tunneling dynamics of phenol photodissociation via its first excited singlet state (S1 ← S0) is investigated quantum mechanically using a three-dimensional model. The lifetimes of several low-lying vibrational states are examined and compared with experiment. The deuteration of the phenoxyl hydrogen is found to dramatically increase the lifetime, attesting to the tunneling nature of the nonadiabatic dissociation. Importantly, it is shown that owing to the conical intersection topography tunneling in this system cannot be described in the standard adiabatic approximation, which eschews the geometric phase effect since the nonadiabatically computed lifetimes, validated by comparison with experiment, differ significantly from those obtained in that limit.

Non-Adiabatic Effects on Excited States of Vinylidene Observed with Slow Photoelectron Velocity-Map Imaging.

High-resolution slow photoelectron velocity-map imaging spectra of cryogenically cooled X̃2B2 H2CC- and D2CC- in the region of the vinylidene triplet excited states are reported. Three electronic bands are observed and, with the assistance of electronic structure calculations and quantum dynamics on ab initio-based near-equilibrium potential energy surfaces, are assigned as detachment to the [Formula: see text] 3B2 (T1), b̃ 3A2 (T2), and à 1A2 (S1) excited states of neutral vinylidene. This work provides the first experimental observation of the à singlet excited state of H2CC. While regular vibrational structure is observed for the ã and à electronic bands, a number of irregular features are resolved in the vicinity of the b̃ band vibrational origin. High-level ab initio calculations suggest that this anomalous structure arises from a conical intersection between the ã and b̃ triplet states near the b̃ state minimum, which strongly perturbs the vibrational levels in the two electronic states through nonadiabatic coupling. Using the adiabatic electron affinity of H2CC previously measured to be 0.490(6) eV by Ervin and co-workers [J. Chem. Phys. 1989, 91, 5974], term energies for the excited neutral states of H2CC are found to be T0(ã 3B2) = 2.064(6), T0(b̃ 3A2) = 2.738(6), and T0(à 1A2) = 2.991(6) eV.

Master Equation Analysis of Thermal and Nonthermal Microwave Effects.

Master equation is a successful model to describe the conventional heating reaction, it is expanded to capture the "microwave effect" in this work. The work equation of "microwave effect" included master equation presents the direct heating, indirect heating, and nonthermal effect about the microwave field. The modified master equation provides a clear physics picture to the nonthermal microwave effect: (1) The absorption and the emission of the microwave, which is dominated by the transition dipole moment between two corresponding states and the intensity of the microwave field, provides a new path to change the reaction rate constants. (2) In the strong microwave field, the distribution of internal states of the molecules will deviate from the equilibrium distribution, and the system temperature defined in the conventional heating reaction is no longer available. According to the general form of "microwave effect" included master equation, a two states model for unimolecular dissociation is proposed and is used to discuss the microwave nonthermal effect particularly. The average rate constants can be increased up to 2400 times for some given cases without the temperature changed in the two states model. Additionally, the simulation of a model system was executed using our State Specified Master Equation package. Three important conclusions can be obtained in present work: (1) A reasonable definition of the nonthermal microwave effect is given in the work equation of "microwave effect" included master equation. (2) Nonthermal microwave effect possibly exists theoretically. (3) The reaction rate constants perhaps can be changed obviously by the microwave field for the non-RRKM and the mode-specified reactions.

Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.

Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.

State-Resolved Quantum Dynamics of Photodetachment of HCO2(-)/DCO2(-) on an Accurate Global Potential Energy Surface.

Full-dimensional quantum dynamics studies of the photodetachment of HCO2(-) and DCO2(-) are reported using a wave-packet method on an accurate global potential energy surface of the neutral HOCO/HCO2 system. The calculated photoelectron spectra reproduced both the positions and widths of the main HCO2 and DCO2 peaks observed in experiment. Specifically, both the (2)A1 and (2)B2 resonance peaks of the neutral radicals were identified in our simulations thanks to the adiabatic PES that captures both the (2)A1 and (2)B2 minima. The narrow widths and isotope effect of the lowest resonances are indicative of tunneling-facilitated predissociation. Furthermore, the dissociation product CO2 was found to be excited in both its symmetric stretching and bending modes, which are coupled via a strong Fermi resonance, but rotationally cold, in good agreement with the recent photoelectron-photodetachment coincidence experiments.

From ab initio potential energy surfaces to state-resolved reactivities: X + H2O ↔ HX + OH [X = F, Cl, and O((3)P)] reactions.

We survey the recent advances in theoretical understanding of quantum state resolved dynamics, using the title reactions as examples. It is shown that the progress was made possible by major developments in two areas. First, an accurate analytical representation of many high-level ab initio points over a large configuration space can now be made with high fidelity and the necessary permutation symmetry. The resulting full-dimensional global potential energy surfaces enable dynamical calculations using either quasi-classical trajectory or more importantly quantum mechanical methods. The second advance is the development of accurate and efficient quantum dynamical methods, which are necessary for providing a reliable treatment of quantum effects in reaction dynamics such as tunneling, resonances, and zero-point energy. The powerful combination of the two advances has allowed us to achieve a quantitatively accurate characterization of the reaction dynamics, which unveiled rich dynamical features such as steric steering, strong mode specificity, and bond selectivity. The dependence of reactivity on reactant modes can be rationalized by the recently proposed sudden vector projection model, which attributes the mode specificity and bond selectivity to the coupling of reactant modes with the reaction coordinate at the relevant transition state. The deeper insights provided by these theoretical studies have advanced our understanding of reaction dynamics to a new level.

Communication: On the competition between adiabatic and nonadiabatic dynamics in vibrationally mediated ammonia photodissociation in its A band.

Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH3(X̃(1)A1), full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH3(X̃(1)A1) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH2(Ã(2)A1)/NH2(X̃(2)B1) branching ratio is found to be small regardless of the initial preparation of NH3(X̃(1)A1), while the internal state distribution of the preeminent fragment, NH2(X̃(2)B1), is found to depend strongly on the initial vibrational excitation of NH3(X̃(1)A1). The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH2(X̃(2)B1) fragment, rather than in NH2(Ã(2)A1) as previously proposed. The high internal excitation of the NH2(X̃(2)B1) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH3. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.