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Direct dynamics by mixed quantum–classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive timesteps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature- driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κTSH). We show how powerful these new methods are in terms of computer time and good agreement with methods employing nonadiabatic coupling vectors computed in conventional ways. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.

The photoinduced ring-opening reaction of 1,3-cyclohexadiene to produce 1,3,5-hexatriene is a classic electrocyclic reaction and is also a prototype for many reactions of biological and synthetic importance. Here, we simulate the ultrafast nonadiabatic dynamics of the reaction in the manifold of the three lowest valence electronic states by using extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2) combined with the curvature-driven coherent switching with decay of mixing (κCSDM) dynamical method. We obtain an excited-state lifetime of 79 fs, and a product quantum yield of 40% from the 500 trajectories initiated in the S

Proton transfer between HOCO+ and CO produces the formyl cation HCO+ and isoformyl cation HOC+ isomers initiating multiple astrochemical reaction networks. Here, the direct chemical dynamics simulations are performed to uncover the underlying atomistic dynamics of the above reaction. The simulations reproduce the measured product energy and scattering angle distributions and reveal that the reaction proceeds predominantly through a direct stripping mechanism which results in the prominent forward scattering observed in experiments. The reaction dynamics show propensity for the HCO+ product even at a collision energy larger than the threshold for HOC+ formation. This is a consequence of the larger opacity and impact parameter range for HCO+. In accordance with the revealed direct mechanistic feature, the reaction can be controlled by orienting the reactants into a reactive H-C orientation that also favors HCO+ formation. Considering the lack of equilibrated reactant complexes and the on the fly migration of the proton, the CO2-catalyzed isomerization is assumed to have insignificant impact on the isomer ratios. This work provides insights of dynamical effects besides energetics into the interesting finding of strongly suppressed formation of the metastable isoformyl cation for related proton transfer reactions in the measurements.

The investigation on evolution of coal char structure during pressurized pyrolysis can reveal the combustion reactivity of coal char in thermal utilization at elevated pressure. In this study, Zhundong subbituminous coal was demineralized and a pressurized drop tube reactor (PDTR) was used to prepare coal char under different temperature and pressure conditions. The physicochemical structures of raw and demineralized coal chars were characterized by the application of nitrogen adsorption analyzer, automatic mercury porosimeter, and Fourier transform infrared spectroscopy (FTIR). The change mechanism of char infrared structure with pyrolysis pressure is revealed on the molecular level in this paper. The results show that the N2 adsorption quantity of raw coal char increases with the increase of pyrolysis temperature, while that of demineralized coal char decreases. Because of the difference in molecular volume and steric hindrance between aliphatic and aromatic structure in char, the increasing pressure has less inhibition effect on the escape of the former than the latter. With the increase of pyrolysis pressure, the combustion reactivity of char is related to the infrared structure at 700 and 800 °C while to macropore structure at 900 and 1000 °C.

As the world’s largest energy consumer (i.e., 24% of the world) and one of the largest biomass resource reserve countries (i.e., total reserves of 73.42 × 108 t a–1), for China, using biomass to pr...

A good understanding of the catalytic mechanism of alkali and alkaline earth metal species during pyrolysis is required for the development of biomass utilization, to take advantage of its special thermochemical properties. The mechanism of the volatile–biochar interaction, especially between H radical/CO2/H2O and K/Ca in biochar, was systematically investigated by combining experimental analyses and density functional theory calculation. The results indicate that, at 500–900 °C, the yield of biochar from rice husk pyrolysis is basically constant, which mainly shows the mutual conversion between gas and liquid products. With the increase of loading alkali and alkaline earth metal species (AAEMs), the tar yield gradually decreased, and with it reaching a certain content, a significant catalytic effect of AAEMs can be observed. K is more beneficial to maintain the stability of the biochar structure than Ca. The intensities of CO and C–O–C functional groups would appear with a certain increase with the increasing concentration of bond-linking AAEMs. At 700–900 °C, the precipitation ratio of K is almost twice that of Ca and even more. The presence of AAEMs can largely inhibit the formation of three-ring tar components, and more converted to one-ring tar components. The H radicals in the volatile can be bonded to C in the C–O–K structure, thereby causing the K element to decouple with the functional group, and tend to be adsorbed on the carbon matrix. For the Ca-loaded structure, it is manifested in strong adsorption of H radicals by Ca, resulting in the weakening of C–O bonds and the looseness of the biochar structure. The interaction between K/Ca in biochar and H2O/CO2 is reflected in the mutual attraction of AAEMs and the O atom in the H2O/CO2 molecule.

This study aims to investigate the effect of pyrolysis pressure on the physical and chemical structure characteristics and reactivity of subbituminous demineralized coal char. The pyrolysis experiments were studied under different pressures using a pressurized drop tube reactor (PDTR). Structural properties of coal chars were investigated by the application of scanning electron microscopy (SEM), nitrogen adsorption analyzer, automatic mercury porosimeter, and Raman spectroscopy, respectively. The Random Pore Model was used to determine kinetic parameters and intrinsic reactivity of chars. The specific pore volume of chars pyrolyzed at 900–1000 °C increased first and then decreased with pyrolysis pressure increasing, and the maximum value of the specific pore volume of chars occurred at 1.0 MPa. The degree of graphitization of chars deepened with the increase of temperature or pressure. Intrinsic activation energy of char-O2 was within the range of 126–134 kJ/mol. The intrinsic reactivity of char-O2 reaction showed strong correlation the Raman parameters with the change of pyrolysis conditions, and it suggested that the intrinsic reactivity of char-O2 reaction was mainly affected by aromatic ring structures rather than pore structures.

Electronically nonadiabatic dynamics methods based on a self-consistent potential, such as semiclassical Ehrenfest and coherent switching with decay of mixing, have a number of advantages but are computationally slower than approximations based on an unaveraged potential because they require evaluation of all components of the nonadiabatic coupling vector. Here we introduce a new approximation to the self-consistent potential that does not have this computational drawback. The new approximation uses time-derivative couplings evaluated by overlap integrals of electronic wave functions to approximate the nonadiabatic coupling terms in the equations of motion. We present a numerical test of the method for ethylene that shows there is little loss of accuracy in the ensemble-averaged results. This new approximation to the self-consistent potential makes direct dynamics calculations with self-consistent potentials more efficient for complex systems and makes them practically affordable for some cases where the cost was previously too high.

The heterogeneous NO reduction characteristics with biomass char and coal char blends in a microfluidized bed reaction analyzer (MFBRA) and its kinetic analysis were investigated. Sawdust char had ...

Barrierless unimolecular association reactions are prominent in atmospheric and combustion mechanisms but are challenging for both experiment and kinetics theory. A key datum for understanding the pressure dependence of association and dissociation reactions is the high-pressure limit, but this is often available experimentally only by extrapolation. Here we calculate the high-pressure limit for the addition of a chlorine atom to acetylene molecule (Cl + C2H2→C2H2Cl). This reaction has outer and inner transition states in series; the outer transition state is barrierless, and it is necessary to use different theoretical frameworks to treat the two kinds of transition state. Here we study the reaction in the high-pressure limit using multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) at the outer transition state and reaction-path variational transition state theory (RP-VTST) at the inner turning point; then we combine the results with the canonical unified statistical (CUS) theory. The calculations are based on a density functional validated against the W3X-L method, which is based on coupled cluster theory with single, double, and triple excitations and a quasiperturbative treatment of connected quadruple excitations [CCSDT(Q)], and the computed rate constants are in good agreement with some of the experimental results. The chlorovinyl (C2H2Cl) adduct has two isomers that are equilibrium structures of a double-well C≡C–H bending potential. Two procedures are used to calculate the vibrational partition function of chlorovinyl; one treats the two isomers separately and the other solves the anharmonic energy levels of the double well. We use these results to calculate the standard-state free energy and equilibrium constant of the reaction.

Direct nonadiabatic dynamics is used to study processes involving multiple electronic states from small molecules to materials. Compared with dynamics with fitted analytical potential energy surfaces, direct dynamics is more user-friendly in that it obtains all needed energies, gradients, and nonadiabatic couplings (NACs) by electronic structure calculations. However, the NAC that is usually used does not conserve angular momentum or the center of mass in widely used mixed quantum-classical nonadiabatic dynamics algorithms, in particular, trajectory surface hopping, semiclassical Ehrenfest, and coherent switching with decay of mixing. We show that by using a projection operator to remove the translational and rotational components of the originally computed NAC, one can restore the conservation.

Methane steam reforming (MSR) is studied experimentally and numerically. The intrinsic kinetics of the reaction are determined using a micro fluidized bed with a catalyst containing more than 50 wt % NiO/α-Al2O3. Intrinsic kinetic models are developed for parallel and serial reaction mechanisms, but the parallel mechanism is found to better match the experimental data. The activation energies for CO and CO2 formation are 81.69 kJ/mol and 59.38 kJ/mol, respectively, and the pre-exponential factors are 316.6 mol/(g h kPa0.85) and 0.00263 mol/(g h kPa3.1), respectively. As the reaction temperature increases, the rate of CO formation increases and that of CO2 decreases. At 800 °C, almost all the CH4 is converted to CO and H2, and the methane conversion rate (XCH4), the hydrogen production rate (YH2), and the CO selectivity (SCO) are 92.28%, 3.34, and 0.99, respectively. The effects of the steam-to-carbon ratio (S/C), inlet velocity, and preheating temperature at different reaction temperatures are simulated using the FLUENT software package. As S/C increases, XCH4 and YH2 increase, but SCO decreases. The higher the reaction temperature, the less S/C promotes XCH4 and YH2. When the reaction temperature is 700 °C and the inlet velocity is 0.2 m/s (residence time is 0.5 s), XCH4 is above 95%, and changes in the inlet velocity strongly influence the formation of CO. With increasing preheating temperature, XCH4, YH2, and SCO all increase gradually.

Fuel conversion and clean energy reaction systems involve a variety of catalytic and non-catalytic gas-solid thermochemical reactions. A good understanding of the correct reaction mechanism and kinetics, as well as the profiles of reaction products, is of great significance to the development, design, and operation of such reaction systems. The micro fluidized bed reaction analysis provides an efficient and reliable method to acquire this essential information with low capital and operating costs, low energy consumption and enhanced safety. This paper provides an overview of the system and its characteristics for the micro fluidized bed reaction analyzer that has been well proven to be a reliable new approach as well as an instrument for characterizing various gas-solid thermochemical reactions.

Oxygen-fuel combustion is a promising technology for CO2 emission reduction. The high-temperature entrained flow reactor and high-temperature drop tube furnace were used to analyses the formation and O2/CO2 combustion characteristics of real-environment coal char in high-temperature oxy-fuel conditions. It proposed “inflection point standard” of high-temperature flame method for the preparation of real-environmental oxy-fuel coal char according to the flame method. The results show that the ratios of C=O/C-O and C=O/Car increase in the coal char compared with the raw coals. The trend of C=O/Car in oxy-fuel condition is opposite to that in the inert atmosphere, due to the effect of high-concentration CO2. To achieve the burnout rate similar to air combustion for coal char, with the increase of coal rank, the O2 concentration should be enhanced. The optimal O2 concentration for the oxy-fuel combustion of JC anthracite is 30%, while that of other low-rank coals could be lower than 30%. The combustion characteristic of JC anthracite is with the highest sensitivity to temperature and O2 concentration.

To investigate pyrolysis characteristics of Shenhua bituminous coal under pressurized conditions, the effects of pressure (0-1.2 MPa) on the physicochemical structure and combustion reactivity of pyrolysis char samples prepared at 1073 and 1273 K were studied in a pressurized drop tube furnace (PDTF). The low temperature nitrogen adsorption test was used to characterize the physical structure of char samples. The results showed that, the increase of pyrolysis pressure is conducive to formation of mesopores, and the specific surface area is larger at 1273K. Raman and XPS analysis were used to characterize the chemical structure of char samples. The results showed that, the increase of pressure can promote the transformation of smaller aromatic structure into larger aromatic structure, and the graphitization degree are more obvious at 1273K. With the increase of pressure, the proportion of C=C/C-C bond in char structure increases and the proportion of C-H bond decreases. It indicates that the unst...

Silica is widely applied in industrial fields due to its good properties, while preparation of high-quality SiO2 by carbonization is an important way to utilize CO2. The experiment was carried out in a microbubble/bubbling experimental device, with its mass transfer kinetics of carbonization analyzed according to the pH-t curves. Under microbubble conditions, with the increasing temperature of 20∼60°C, the specific surface area, oil absorption value and particle size of silica varies at 336.80∼231.29 m2/g, 1.12∼1.81 ml/g and 16.49∼14.60 μm, respectively, which is similar as that with bubble. Aging at 20∼90 °C, they involve in the range of 35.82∼128.76 m2/g, 1.59∼2.44 ml/g and 23.15∼14.46 μm. With total concentration of solution >0.5 M, the concentration increases, the specific surface area and particle size of microbubbles are larger than those of the bubbling silica, and oil absorption value increases at 1.81∼2.44 ml/g. The kinetic analysis shows that it is more consistent with theoretical value, which can be judged as the secondary-reaction process. The microbubbles increase the CO2 utilization rate and volumetric mass transfer coefficient of carbonization by 2-4 times, while the liquid-phase mass transfer coefficient decreases. It indicates that microbubble mass transfer is achieved by significantly increasing the specific surface area.