Prediction Of Reaction Rate Constants Research Articles

Transfer Learning Approach to Multitarget Temperature-Dependent Reaction Rate Prediction.

Accurate prediction of temperature-dependent reaction rate constants of organic compounds is of great importance to both atmospheric chemistry and combustion science. Extensive work has been done on developing automated mechanism generation systems but the lack of quality reaction rate data remains a huge bottleneck in the application of highly detailed mechanisms. Machine learning prediction models have been recently adopted to alleviate the data gap in thermochemistry and have great potential to do the same for kinetic data with the recent release of quality reaction rate data compilations. The ultimate goal is to formulate easily accessible, general-purpose, temperature-dependent, and multitarget models for the prediction of reaction rates. To that end, we propose a model that depends on the well-known Morgan fingerprints as well as learned representations transferred from the QM9 data set. We propose the use of an Arrhenius-based loss where predictions of the three modified-Arrhenius parameters (A, n, and B = Ea/R) are given instead of the direct prediction of reaction rate constants. Our model is >35% more accurate compared to a baseline model of feed forward network (FFN) on Morgan fingerprints.

Prediction of reaction rate constants of hydroxyl radical with chemicals in water.

The rate constants (kOH ) of the reactions between organic micropollutants with hydroxyl radical (•OH) in aqueous systems are an important parameter to evaluate the persistence of organic compounds in the environment. In this paper, a support vector machine (SVM) model based on five descriptors was built to predict the reaction rate constants (logK=(logkOH )/MW ). The quantitative structure-activity relationship (QSAR) model of logK was obtained from a training set (600 compounds) and validated with a test set (395 compounds). The coefficients of determination R2 of the training and test sets are 0.923 and 0.925, respectively. The results suggest that the SVM model developed in this work possesses satisfactory prediction ability. PRACTITIONER POINTS: The rate constants of the reactions of organic micropollutants with •OH in aqueous systems were investigated. SVM model was established for the reaction rate constants (logK=(logkOH )/MW ). Only five molecular descriptors were used to predict 995 logK. A large data set was used for the test set (395 compounds).

A Monte Carlo method based QSPR model for prediction of reaction rate constants of hydrated electrons with organic contaminants

ABSTRACT The Monte Carlo algorithm was applied to formulate a robust quantitative structure–property relationship (QSPR) model to compute the reactions rate constants of hydrated electron values for a data set of 309 water contaminants containing 125 aliphatic and 184 phenyl-based chemicals. The QSPR models were computed with the hybrid optimal descriptors which were procured by combining the SMILES and hydrogen-suppressed molecular graph for both classes of compounds. Approximately 75% of the total experimental data set was randomly divided into training and invisible training sets, while approximately 25% was divided into calibration and validation sets. The authenticity and robustness of the developed QSPR models were also judged by the Index of Ideality of Correlation. In QSPR modelling of aliphatic compounds, the numerical values of , , and were in the range of 0.852–0.905, 0.815–0.894, 0.839–0.897 and 0.737–0.867, respectively. Whereas, in the QSPR modelling of phenyl-based compounds, the numerical values of , , and were in the range of 0.867–0.896, 0.852–0.865, 0.816–0.850 and 0.760–0.762, respectively. The structural attributes, which are promoters of increase/decrease are also extracted from the SMILES notation for mechanistic interpretation. These QSPR models can also be applied to compute the reaction rate constants of organic contaminants.

Ab initio kinetics predictions for H-atom abstraction from diethoxymethane by hydrogen, methyl, and ethyl radicals and the subsequent unimolecular reactions

Diethoxymethane (DEM) is a promising oxygenated fuel and fuel additive, which has similar positive combustion characteristics as dimethoxymethane. DEM contains C−C bonds and can form ethylene via β-scission, which potentially increases its sooting tendency. Since DEM is rarely studied, however, kinetic modeling attempts are forced to rely on rate constant analogies. Therefore, we employ high level CCSD(T)/aug-cc-pV(T+D)Z//B2PLYPD3BJ/6-311++(d,p) theory along with transition state theory to predict reaction rate constants for H-abstraction by H˙ and C˙H3 and the subsequent unimolecular reactions. We further prove that the DLPNO approximation to CCSD(T) leads to a deviation of less than 0.25 k/mol in barrier heights for the presently studied open-shell electronic structures and use it for the prediction of reaction rate constants for H-abstraction by C˙2H5 radicals. We find that H-abstraction by ethyl radicals might denote a significant pathway, which should not be neglected in kinetic modeling studies of DEM. It is also shown that reaction pathways leading to ethylene formation are of minor importance and give thereby a first insight into the fate of the C−C bonds. To the best of our knowledge, this study represents the first high-level ab-initio study of DEM, which makes the reaction kinetics and thermochemistry data provided by this study vital for future comprehensive kinetic modeling of DEM.

Computational Prediction of Rate Constants for Reactions Involved in Al Clustering.

Aluminum (Al) clustering processes via three types of association reactions are herein studied using classical molecular dynamics trajectory calculations. The simulations were carried out under realistic experimental conditions. The dependence of rate constants on temperature and cluster size was obtained. The association reactions have a very small activation barrier, and the activation energy increases with increasing temperature. Our prediction of reaction rate constants can be of interest for the study of Al nanoparticle growth using kinetic models.

Ab Initio Calculation of Rate Constants for Molecule-Surface Reactions with Chemical Accuracy.

The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude).

Ab Initio Calculation of Rate Constants for Molecule–Surface Reactions with Chemical Accuracy

AbstractThe ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude).

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91∕6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + (3)O(2) via the direct triplet abstraction path and ClO + NO(2) via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO(2) intermediates. The yield of ClNO + O(2) ((1)△) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + (3)O(2) and ClO + NO(2) production from ClOO + NO can be given by 2.66 × 10(-16) T(1.91) exp(341/T) (200-700 K) and 1.48 × 10(-24) T(3.99) exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO(2) in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results.

Water Clusters on Graphite: Methodology for Quantum Chemical A Priori Prediction of Reaction Rate Constants

The properties, interactions, and reactions of cyclic water clusters (H(2)O)(n=1-5) on model systems for a graphite surface have been studied using pure B3LYP, dispersion-augmented density functional tight binding (DFTB-D), and integrated ONIOM(B3LYP:DFTB-D) methods. Coronene C(24)H(12) as well as polycircumcoronenes C(96)H(24) and C(216)H(36) in monolayer, bilayer, and trilayer arrangements were used as model systems to simulate ABA bulk graphite. Structures, binding energies, and vibrational frequencies of water clusters on mono- and bilayer graphite models have been calculated, and structural changes and frequency shifts due to the water cluster-graphite interactions are discussed. ONIOM(B3LYP:DFTB-D) with coronene and water in the high level and C(96)H(24) in the low level mimics the effect of extended graphite pi-conjugation on the water-graphite interaction very reasonably and suggests that water clusters only weakly interact with graphite surfaces, as suggested by the fact that water is an excellent graphite lubricant. We use the ONIOM(B3LYP:DFTB-D) method to predict rate constants for model pathways of water dissociative adsorption on graphite. Quantum chemical molecular dynamics (QM/MD) simulations of water clusters and water addition products on the C(96)H(24) graphite model are presented using the DFTB-D method. A three-stage strategy is devised for a priori investigations of high temperature corrosion processes of graphite surfaces due to interaction with water molecules and fragments.

Kinetics and mechanisms for reactions of HNO with CH3 and C6H5 studied by quantum‐chemical and statistical‐theory calculations

AbstractKinetics and mechanisms for the reactions of HNO with CH3 and C6H5 have been investigated by ab initio molecular orbital (MO) and transition‐state theory (TST) and/or Rice‐Ramsperger‐Kassel‐Marcus/Master Equation (RRKM/ME) calculations. The G2M(RCC, MP2)//B3LYP/6‐31G(d) method was employed to evaluate the energetics for construction of their potential energy surfaces and prediction of reaction rate constants. The reactions R + HNO (R = CH3 and C6H5) were found to proceed by two key product channels giving (1) RH + NO and (2) RNO + H, primarily by direct abstraction and indirect association/decomposition mechanisms, respectively. As both reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our TST and RRKM/ME calculations. For practical applications, the rate constants evaluated for the atmospheric‐pressure condition are represented by modified Arrhenius equations in units of cm3 mol−1 s−1 for the temperature range 298–2500 K: κ1A = 1.47 × 1011T0.76 exp[−175/T], κ2A = 8.06 × 103T2.40 exp[−3100/T], κ1B = 3.78 × 105T2.28 exp[230/T], and κ2B = 3.79 × 109T1.19 exp[−4800/T], where A and B represent CH3 and C6H5 reactions, respectively. Based on the predicted rate constant at 1 atm pressure for R + HNO → RNO + H, we estimated their reverse rate constants for R + HNO production from H + RNO in units of cm3 mol−1 s−1: κ−2A′ = 7.01 × 1010 T0.84 exp[120/T] and κ−2B′ = 2.22 × 1019 T−1.01 exp[−9700/T]. The heats of formation at 0 K for CH3NO, CH3N(H)O, CH3NOH, C6H5N(H)O, and C6H5NOH have been estimated to be 18.6, 18.1, 22.5, 47.2, and 50.7 kcal mol−1 with an estimated ±1 kcal mol−1 error. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 261–274, 2005