High-level Theory Research Articles

Accelerating Real-Time Coupled Cluster Methods with Single-Precision Arithmetic and Adaptive Numerical Integration.

We explore the framework of a real-time coupled cluster method with a focus on improving its computational efficiency. Propagation of the wave function via the time-dependent Schrödinger equation places high demands on computing resources, particularly for high level theories such as coupled cluster with polynomial scaling. Similar to earlier investigations of coupled cluster properties, we demonstrate that the use of single-precision arithmetic reduces both the storage and multiplicative costs of the real-time simulation by approximately a factor of 2 with no significant impact on the resulting UV/vis absorption spectrum computed via the Fourier transform of the time-dependent dipole moment. Additional speedups─of up to a factor of 14 in test simulations of water clusters─are obtained via a straightforward GPU-based implementation as compared to conventional CPU calculations. We also find that further performance optimization is accessible through sagacious selection of numerical integration algorithms, and the adaptive methods, such as the Cash-Karp integrator, provide an effective balance between computing costs and numerical stability. Finally, we demonstrate that a simple mixed-step integrator based on the conventional fourth-order Runge-Kutta approach is capable of stable propagations even for strong external fields, provided the time step is appropriately adapted to the duration of the laser pulse with only minimal computational overhead.

Quantum Inelastic Scattering of ArHAr+, HeHHe+, and NeHNe+ with He on New Potential Energy Surfaces

The recent interstellar detections of ArH+ and HeH+ have increased the interest in noble molecules. In this work, we develop potential energy surfaces (PESs) at a high level of theory for the HeHHe+ + He, ArHAr+ + He, and NeHNe+ + He complexes and study the collision dynamics. A large number of ab initio energies are computed at the coupled-cluster with single, double, and perturbative triple excitations level of theory for the systems. A grid of energies at the complete basis set limit is fitted to an analytical function for each complex. These PESs are then employed in close-coupling calculations at low collision energies. The rotational state-to-state rate coefficients of HeHHe+ by collision He are compared with previous studies, and an excellent agreement is found. Furthermore, the available quenching rate coefficients for ArH+, HeH+, and NeH+, by He, are compared with those computed in this work, and the rotational de-excitations of the diatoms are more efficient than with the triatomic systems. Finally, a set of rate coefficients for ArHAr+ + He, HeHHe+ + He, and NeHNe+ + He at low temperatures is reported.

Quantum study of the bending relaxation of H2O by collision with H

ABSTRACT Vibrationally excited levels of the H2O molecule are currently detected in various environments of the interstellar medium (ISM), and collisional data for H2O, including vibration with the main colliders of the ISM, are needed. The present study focuses on the bending relaxation of H2O by collision with H when taking bending–rotation coupling explicitly into account with the rigid-bender close-coupling (RB-CC) method. With this aim, a new four-dimensional potential energy surface including the H2O bending mode is developed from a large grid of ab initio energies computed using a high level of theory. For purely rotational transitions, our RB-CC rates show very good agreement with rigid-rotor calculations performed using our new potential energy surface (PES) and with those available in the literature. Calculations for pure rotational transitions inside the excited bending level ν2 = 1 of H2O are performed and compared with their equivalents inside ν2 = 0. Vibrational quenching of H2O is also calculated and found to be much more efficient through collision with H rather than with He.

Solvent Cage Concept for the Homolytic Fragmentation of the Peroxynitrite-CO2 Adduct, ONOOCO2.

The toxicity of peroxynitrite, ONOO-, is directed by carbon dioxide via the formation of the corresponding adduct, ONOOCO2-. Entity ONOOCO2- is believed to be a highly unstable compound that primarily decomposes to nitrate and carbon dioxide, but it also undergoes fractional homolysis to generate carbonate radical anion, CO3•-, and nitrogen dioxide, NO2•, in a so-called solvent (radical) cage reaction. Recently, Koppenol et al. reviewed their proposal that ONOOCO2- is a relatively long-lived intermediate, arguing that "the solvent cage as proposed is physically not realistic". To further address whether ONOOCO2- could be a long-lived species, bond dissociation enthalpies (BDE) were calculated by the composite reference method (SMD)W1BD. Anion ONOOCO2- can exist in two conformers, s-cis-gauche and s-trans-gauche with predicted gas-phase O-O BDEs of about 10.8 and 9.5 kcal mol-1, respectively. Therefore, both conformers should have very short lifetimes. The (SMD)W1BD method was also used to evaluate the thermodynamic parameters of interest, revealing that the homolytic decomposition of ONOOCO2- is the most reasonable pathway. Moreover, previously reported experimental chemically induced dynamic nuclear polarization data also support the intermediacy of the radical cage and the formation of products CO2 and NO3- at a total yield of about 70%. Because the solvent radical cage concept for the decay of ONOO- in the presence of CO2 is supported by a variety of spectrometric methods as well as by quantum chemical calculations at high levels of theory, it provides strong evidence against the "out-of-cage" construct. For clarification of the nature of the transient UV/vis absorption(s) between 600 and 700 nm, as observed by Koppenol et al., several experimental approaches are suggested.

Toward High-level Machine Learning Potential for Water Based on Quantum Fragmentation and Neural Networks.

Accurate and efficient simulation of liquids, such as water and salt solutions, using high-level wave function theories is still a formidable task for computational chemists owing to the high computational costs. In this study, we develop a deep machine learning potential based on fragment-based second-order Møller-Plesset perturbation theory (DP-MP2) for water through neural networks. We show that the DP-MP2 potential predicts the structural, dynamical, and thermodynamic properties of liquid water in better agreement with the experimental data than previous studies based on density functional theory (DFT). The nuclear quantum effects (NQEs) on the properties of liquid water are also examined, which are noticeable in affecting the structural and dynamical properties of liquid water under ambient conditions. This work provides a general framework for quantitative predictions of the properties of condensed-phase systems with the accuracy of high-level wave function theory while achieving significant computational savings compared to ab initio simulations.

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules.

The chemiluminescent reactions of the group 3 metals Sc and Y with F2, Cl2, Br2, ClF, ICl (Sc), IBr (Y), and SF6 and La with F2, SF6, Cl2, and ClF have been studied at low pressures (6 × 10-6 to 4 × 10-4 Torr) using a beam-gas arrangement and extended to the 10-3 Torr multiple collision pressure range. Contrary to previous reports, the observed chemiluminescent spectra are primarily attributed to emission from the metal monohalides. Extensive pressure and temperature dependence studies and high-level correlated molecular orbital theory calculations of the bond dissociation energies support this conclusion and the attribution of the chemiluminescence. Evidence for the "selective" production of a monohalide excited electronic state is obtained for several of the Sc and Y reactions. All reactions producing the metal monofluorides are first order with respect to the oxidant, while reactions producing the monochlorides and monobromides are found to be "faster than first order" with respect to the oxidant. This difference is associated with the metal halide bond dissociation energies and the metal halide product internal density of states. Analysis of the temperature dependence for six representative reactions indicates that the "selective" excited-state formation of the metal monohalides proceeds via a direct mechanism with negligible activation energy. We compare and contrast the present results with previous experiments and interpretations which have assigned the selective emission from these systems to the group 3 dihalides produced in a two-step reaction sequence analogous to an electron jump process. The current results suggest a distinctly different interpretation of the observed processes in these systems. The observed selectivity observed in these studies is remarkable given the significant number of known and potential excited states in the scandium and yttrium halides as well as their different electronic configurations.

Copper-mediated aromatic fluorination using N-heterocycle-carbene ligand: Free energy profile of the Cu(I)/Cu(III) and Cu(II) radical mechanisms

Addition of fluorine to organic molecules in the late stage of synthesis has been an increased interest in the past decade. Catalytic methods using fluoride salts as reagents could be especially useful, mainly with the use of organometallic catalysis with copper. Recent experimental advances have been reported for copper-mediated fluorination and the development of an efficient catalytic process needs a deep understanding of the reaction mechanism and the free energy profile. In this work, different mechanisms of copper-mediated fluorination of 2-(2-bromophenyl)pyridine using LCuF as reagent (L = N-heterocycle-carbene ligand) were investigated using very high level of theory, DLPNO-CCSD(T) method with up to quadruple-zeta basis set. The Cu(I)/Cu(III) mechanism is the predominant one, taking place via neutral (MS2) or cationic (MS2p) intermediates. Although the oxidative addition step has high barrier, the reductive elimination was found to be the rate-determining step. Three reaction pathways involving the Cu(II) radical mechanism was also investigated. The first one is the single-electron transfer mechanism and the second is the bromine atom transfer in the first step. Both pathways involve high free energy intermediates and are inviable. The third mechanism occurs via singlet-triplet spin crossover with bromine transfer from the oxidative addition intermediate MS2 to the LCuF initial reagent. However, the reductive elimination step from the MS2r doublet Cu(II) complex is much more difficult than the MS2 or MS2p singlets of Cu(III) complexes, leading to a very slow kinetics for this Cu(II) radical mechanism. The kinetics analysis of the theoretical free energy profile results in effective ΔG‡ of 30.6 kcal mol−1, in good agreement with an estimated experimental value and providing an important support for the Cu(I)/Cu(III) mechanism.

Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations.

Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf-O or Hf-B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cluster quantum chemical calculations on these systems. We compute full potential energy curves, excitation energies, ionization energies, electronic configurations, and spectroscopic parameters with large quadruple-ζ and quintuple-ζ quality correlation consistent basis sets. We also investigate equilibrium chemical bonding patterns and effects of correlating core electrons on property predictions. Differences in the ground state electron configuration of HfB(X4Σ-) and HfO(X1Σ+) lead to a significantly stronger bond in HfO than HfB, as judged by both dissociation energies and equilibrium bond distances. We extend our analysis to the chemical bonding patterns of the isovalent HfX (X = O, S, Se, Te, and Po) series and observe similar trends. We also note a linear trend between the decreasing value of the dissociation energy (De) from HfO to HfPo and the singlet-triplet energy gap (ΔES-T) of the molecule. Finally, we compare these benchmark results to those obtained using density functional theory (DFT) with 23 exchange-correlation functionals spanning multiple rungs of "Jacob's ladder." When comparing DFT errors to coupled cluster reference values on dissociation energies, excitation energies, and ionization energies of HfB and HfO, we observe semi-local generalized gradient approximations to significantly outperform more complex and high-cost functionals.

Structural and spectroscopic study of neutral dioxides MO2 (M = B, Al, Ga, In, Tl)

Both ab initio Hartree-Fock self consistent field (HF-SCF) with Cluster Coupled (CCSD(T)) and Density Functional Theory with B3LYP functional, high level theories are adopted for structural study of different dioxides MO2 (M = B, Al, Ga, In and Tl). A geometry optimization is performed using the avtz, aug-cc-pwcvnz (nz = tz; qz; 5z), 6–311++G** and Lanl2DZ basis sets. Vibration frequencies are reported for optimized geometries. We also report calculated M-O and O-O bond lengths, O-M-O and M-O-O, bond angles for stable isomers. Our calculations indicate that there are five possible isomers with linear or folded shapes. Some discrepancies with previous results are noted, on the other hand, according to our CCSD(T) calculations, MO2 molecule (M = B, Al and Ga) is in ground state when it is linear and symmetric O-M-O (2Πg), then in a higher energy state with the cyclic isomer (2A2, or 2A1) and in more higher state when it is dissymmetric M-O-O (2A’, 2∑+), B3LYP and CCSD(T) results agree on energetic ordering of various isomeric forms for BO2, AlO2,InO2 and TlO2 systems, while there is disagreement for GaO2, molecule. HOMO-1, HOMO, LUMO and LUMO + 1 molecular orbitals for the most stable structures are given as well. NBO analysis is performed to study the superoxide 2A2 and its stability which evolves according to electropositivity of metal along the 13th column of periodic table.

Self-Consistent Parameterization of DNA Residues for the Non-Polarizable AMBER Force Fields.

Fixed-charge (non-polarizable) forcefields are accurate and computationally efficient tools for modeling the molecular dynamics of nucleic acid polymers, particularly DNA, well into the µs timescale. The continued utility of these forcefields depends in part on expanding the residue set in step with advancing nucleic acid chemistry and biology. A key step in parameterizing new residues is charge derivation which is self-consistent with the existing residues. As atomic charges are derived by fitting against molecular electrostatic potentials, appropriate structural models are critical. Benchmarking against the existing charge set used in current AMBER nucleic acid forcefields, we report that quantum mechanical models of deoxynucleosides, even at a high level of theory, are not optimal structures for charge derivation. Instead, structures from molecular mechanics minimization yield charges with up to 6-fold lower RMS deviation from the published values, due to the choice of such an approach in the derivation of the original charge set. We present a contemporary protocol for rendering self-consistent charges as well as optimized charges for a panel of nine non-canonical residues that will permit comparison with literature as well as studying the dynamics of novel DNA polymers.

A Brain-Inspired Theory of Mind Spiking Neural Network for Reducing Safety Risks of Other Agents.

Artificial Intelligence (AI) systems are increasingly applied to complex tasks that involve interaction with multiple agents. Such interaction-based systems can lead to safety risks. Due to limited perception and prior knowledge, agents acting in the real world may unconsciously hold false beliefs and strategies about their environment, leading to safety risks in their future decisions. For humans, we can usually rely on the high-level theory of mind (ToM) capability to perceive the mental states of others, identify risk-inducing errors, and offer our timely help to keep others away from dangerous situations. Inspired by the biological information processing mechanism of ToM, we propose a brain-inspired theory of mind spiking neural network (ToM-SNN) model to enable agents to perceive such risk-inducing errors inside others' mental states and make decisions to help others when necessary. The ToM-SNN model incorporates the multiple brain areas coordination mechanisms and biologically realistic spiking neural networks (SNNs) trained with Reward-modulated Spike-Timing-Dependent Plasticity (R-STDP). To verify the effectiveness of the ToM-SNN model, we conducted various experiments in the gridworld environments with random agents' starting positions and random blocking walls. Experimental results demonstrate that the agent with the ToM-SNN model selects rescue behavior to help others avoid safety risks based on self-experience and prior knowledge. To the best of our knowledge, this study provides a new perspective to explore how agents help others avoid potential risks based on bio-inspired ToM mechanisms and may contribute more inspiration toward better research on safety risks.

Optimizing the Calculation of Free Energy Differences in Nonequilibrium Work SQM/MM Switching Simulations.

A key step during indirect alchemical free energy simulations using quantum mechanical/molecular mechanical (QM/MM) hybrid potential energy functions is the calculation of the free energy difference ΔAlow→high between the low level (e.g., pure MM) and the high level of theory (QM/MM). A reliable approach uses nonequilibrium work (NEW) switching simulations in combination with Jarzynski’s equation; however, it is computationally expensive. In this study, we investigate whether it is more efficient to use more shorter switches or fewer but longer switches. We compare results obtained with various protocols to reference free energy differences calculated with Crooks’ equation. The central finding is that fewer longer switches give better converged results. As few as 200 sufficiently long switches lead to ΔAlow→high values in good agreement with the reference results. This optimized protocol reduces the computational cost by a factor of 40 compared to earlier work. We also describe two tools/ways of analyzing the raw data to detect sources of poor convergence. Specifically, we find it helpful to analyze the raw data (work values from the NEW switching simulations) in a quasi-time series-like manner. Principal component analysis helps to detect cases where one or more conformational degrees of freedom are different at the low and high level of theory.

Computational materials discovery for lanthanide hydrides at high pressure for high temperature superconductivity

Hydrogen-rich superhydrides are believed to be very promising high critical temperature (high ${T}_{c}$) superconductors, with experimentally observed critical temperatures near room temperature, as shown in recently discovered lanthanide superhydrides at very high pressures, e.g., ${\mathrm{LaH}}_{10}$ at 170 GPa and ${\mathrm{CeH}}_{9}$ at 150 GPa. With the motivation of discovering new hydrogen-rich high ${T}_{c}$ superconductors at the lowest possible pressure, quantitative theoretical predictions are needed. In these promising compounds, superconductivity is mediated by the highly energetic lattice vibrations associated with hydrogen and their interplay with the electronic structure, requiring fine descriptions of the electronic properties, notoriously challenging for correlated $f$ systems. In this paper, we propose a first-principles calculation platform with the inclusion of many-body corrections to evaluate the detailed physical properties of the Ce-H system and to understand the structure, stability, and superconductivity of ${\mathrm{CeH}}_{9}$ at high pressure. We report how the calculation of ${T}_{c}$ is affected by the hierarchy of many-body corrections and obtain a compelling increase in ${T}_{c}$ at the highest level of theory, which goes in the direction of experimental observations. Our findings shed significant light on the search for superhydrides in close similarity with atomic hydrogen within a feasible pressure range. We provide a practical platform to further investigate and understand conventional superconductivity in hydrogen-rich superhydrides.

High-Accuracy Semiempirical Quantum Models Based on a Minimal Training Set.

A great need exists for computationally efficient quantum simulation approaches that can achieve an accuracy similar to high-level theories at a fraction of the computational cost. In this regard, we have leveraged a machine-learned interaction potential based on Chebyshev polynomials to improve density functional tight binding (DFTB) models for organic materials. The benefit of our approach is two-fold: (1) many-body interactions can be corrected for in a systematic and rapidly tunable process, and (2) high-level quantum accuracy for a broad range of compounds can be achieved with ∼0.3% of data required for one advanced deep learning potential. Our model exhibits both transferability and extensibility through comparison to quantum chemical results for organic clusters, solid carbon phases, and molecular crystal phase stability rankings. Our efforts thus allow for high-throughput physical and chemical predictions with up to coupled-cluster accuracy for systems that are computationally intractable with standard approaches.

Laser-Controlled Implementation of Controlled-NOT, Hadamard, SWAP, and Pauli Gates as Well as Generation of Bell States in a 3d-4f Molecular Magnet.

Using high-level ab initio many-body theory, we theoretically propose that the Dy and the Ni atoms in the [Dy2Ni2(L)4(NO3)2(DMF)2] real molecular magnet as well as in its core, that is, the [Dy2Ni2O6] system, act as two-level qubit systems. Despite their spatial proximity we can individually control each qubit in this highly correlated real magnetic system through specially designed laser-pulse combinations. This allows us to prepare any desired two-qubit state and to build several classical and quantum logic gates, such as the two-qubit (binary) CNOT gate with three distinct laser pulses. Other quantum logic gates include the single-qubit (unary) quantum X, Y, and Z Pauli gates; the Hadamard gate (which necessitates the coherent quantum superposition of two many-body electronic states); and the SWAP gate (which plays an important role in Shor's algorithm for integer factorization). Finally, by sequentially using the achieved CNOT and Hadamard gates we are able to obtain the maximally entangled Bell states, for example, ()(|00⟩ + |11⟩).

Large Pressure Effects Caused by Internal Rotation in the s-cis-syn-Acrolein Stabilized Criegee Intermediate at Tropospheric Temperature and Pressure.

Criegee intermediates are important atmospheric oxidants, and quantitative kinetics for stabilized Criegee intermediates are key parameters for atmospheric modeling but are still limited. Here we report barriers and rate constants for unimolecular reactions of s-cis-syn-acrolein oxide (scsAO), in which the vinyl group makes it a prototype for Criegee intermediates produced in the ozonolysis of isoprene. We find that the MN15-L and M06-2X density functionals have CCSD(T)/CBS accuracy for the unimolecular cyclization and stereoisomerization of scsAO. We calculated high-pressure-limit rate constants by the dual-level strategy that combines (a) high-level wave function-based conventional transition-state theory (which includes coupled-cluster calculations with quasiperturbative inclusion of quadruple excitations because of the strongly multiconfigurational character of the electronic wave function) and (b) canonical variational transition-state theory with small-curvature tunneling based on a validated density functional. We calculated pressure-dependent rate constants both by system-specific quantum Rice-Ramsperger-Kassel theory and by solving the master equation. We report rate constants for unimolecular reactions of scsAO over the full range of atmospheric temperature and pressure. We found that the unimolecular reaction rates of this larger-than-previously studied Criegee intermediate depend significantly on pressure. Particularly, we found that falloff effects decrease the effective unimolecular cyclization rate constant of scsAO by about a factor of 3, but the unimolecular reaction is still the dominant atmospheric sink for scsAO at low altitudes. The large falloff caused by the inclusion of the stereoisomerization channel in the master equation calculations has broad implications for mechanistic analysis of reactions with competitive internal rotations that can produce stable rotamers.

Abinitio determination of the polarizability of neon

The static electric-dipole polarizability $\ensuremath{\alpha}$ of the neon atom was determined with a relative uncertainty of only about 0.003% using state-of-the-art ab initio approaches. The new value, $\ensuremath{\alpha}=2.661\phantom{\rule{0.16em}{0ex}}067(77)\phantom{\rule{0.16em}{0ex}}\mathrm{a}.\mathrm{u}.$, is almost five times more accurate than the previous ab initio estimate, $\ensuremath{\alpha}=2.660\phantom{\rule{0.16em}{0ex}}80(36)\phantom{\rule{0.16em}{0ex}}\mathrm{a}.\mathrm{u}.$, by Lesiuk et al. [Phys. Rev. A 102, 052816 (2020)]. Similar to their work, we calculated $\ensuremath{\alpha}$ using ab initio methods up to full configuration interaction and added corrections for finite nuclear mass and size, relativistic, and quantum electrodynamics (QED) effects. The uncertainty reduction of this work was achieved in particular by employing extremely large basis sets, including newly developed ones of 11Z, 12Z, and 13Z quality. Moreover, the finite nuclear mass effects and most of the relativistic contributions were calculated at much higher levels of theory than in the work of Lesiuk et al. However, we adopted their values for the orbit-orbit part of the relativistic correction and for the Bethe logarithm needed to compute the QED correction. The uncertainty of our final value is still an order of magnitude larger than that of the experimental value recently measured by Gaiser and Fellmuth [Phys. Rev. Lett. 120, 123203 (2018)] with an uncertainty of only a few parts per million using dielectric-constant gas thermometry. Yet, our ab initio value agrees with their value, ${\ensuremath{\alpha}}_{\mathrm{exp}}=2.661\phantom{\rule{0.16em}{0ex}}057(7)\phantom{\rule{0.16em}{0ex}}\mathrm{a}.\mathrm{u}.$, almost within the experimental uncertainty. This could indicate that the higher-order relativistic corrections and QED contributions, which dominate our uncertainty budget, are more accurate than expected considering the uncontrolled approximations involved in their calculation.

On-The-Fly Kinetics of the Hydrogen Abstraction by Hydroperoxyl Radical: An Application of the Reaction Class Transition State Theory.

A Reaction Class Transition State Theory (RC-TST) is applied to calculate thermal rate constants for hydrogen abstraction by OOH radical from alkanes in the temperature range of 300–2500 K. The rate constants for the reference reaction C2H6 + ∙OOH → ∙C2H5 + H2O2, is obtained with the Canonical Variational Transition State Theory (CVT) augmented with the Small Curvature Tunneling (SCT) correction. The necessary parameters were obtained from M06-2X/aug-cc-pVTZ data for a training set of 24 reactions. Depending on the approximation employed, only the reaction energy or no additional parameters are needed to predict the RC-TST rates for other class representatives. Although each of the reactions can in principle be investigated at higher levels of theory, the approach provides a nearly equally reliable rate constant at a fraction of the cost needed for larger and higher level calculations. The systematic error is smaller than 50% in comparison with high level computations. Satisfactory agreement with literature data, augmented by the lack of necessity of tedious and time consuming transition state calculations, facilitated the seamless application of the proposed methodology to the Automated Reaction Mechanism Generators (ARMGs) programs.

Pure State v-Representability of Density Matrix Embedding Theory.

Density matrix embedding theory (DMET) formally requires the matching of density matrix blocks obtained from high-level and low-level theories, but this is sometimes not achievable in practical calculations. In such a case, the global band gap of the low-level theory vanishes, and this can require additional numerical considerations. We find that both the violation of the exact matching condition and the vanishing low-level gap are related to the assumption that the high-level density matrix blocks are noninteracting pure-state v-representable (NI-PS-V), which assumes that the low-level density matrix is constructed following the Aufbau principle. To relax the NI-PS-V condition, we develop an augmented Lagrangian method to match the density matrix blocks without referring to the Aufbau principle. Numerical results for the 2D Hubbard and hydrogen model systems indicate that, in some challenging scenarios, the relaxation of the Aufbau principle directly leads to exact matching of the density matrix blocks, which also yields improved accuracy.

HȮ2 + HȮ2: High level theory and the role of singlet channels

At low temperatures and high pressures, the HȮ2 + HȮ2 reaction is an important reaction in combustion. There are significant unresolved discrepancies between prior theoretical and experimental studies of this reaction. It has generally been presumed to occur as an abstraction on the triplet surface to produce H2O2 + 3O2. We employ a combination of high-level electronic structure theory (the ANL0 composite method or multi-reference methods as appropriate), sophisticated transition state theory (vibrationally adiabatic torsions, variational, and variable reaction coordinate), and master equation analyses to predict the thermal kinetics on the H2O4 surface. Notably, this analysis suggests a significant branching to HȮ3 + ȮH near 1000 K via reaction on the singlet surface. This channel does not appear to have been considered in prior combustion models. HȮ3 itself is a metastable complex (bound by only 3 kcal mol–1) that rapidly dissociates to ȮH + 3O2. Thus, the net reaction for this channel, HȮ2 + HȮ2 → ȮH + ȮH + O2, converts two low reactivity HȮ2 radicals into two highly reactive ȮH radicals. The ramifications of these newly derived rate expressions are highlighted through kinetic modeling studies of H2, CH3OH, n-heptane, and isooctane oxidation; all at the high pressures of relevance to combustion devices.