The 50 most-cited articles in The Journal of Physical Chemistry A, 2023

Energy decomposition analysis (EDA) is an important class of methods to explore the nature of interaction between fragments in a chemical system. It can decompose the interaction energy into different physical components to understand the factors that play key roles in the interaction. This work proposes an EDA strategy based on dispersion-corrected density functional theory (DFT), called sobEDA. This method is fairly easy to implement and very universal. It can be used to study weak interactions, chemical bond interactions, open-shell systems, and interactions between multiple fragments. The total time consumption of sobEDA is only about twice that of conventional DFT single-point calculation for the entire system. This work also proposes a variant of the sobEDA method named sobEDAw, which is designed specifically for decomposing weak interaction energies. Through a proper combination of DFT correlation energy and dispersion correction term, sobEDAw gives a ratio between dispersion energy and electrostatic energy that is highly consistent with the symmetry-adapted perturbation…

Advances in machine learned interatomic potentials (MLIPs), such as those using neural networks, have resulted in short-range models that can infer interaction energies with near ab initio accuracy and orders of magnitude reduced computational cost. For many atom systems, including macromolecules, biomolecules, and condensed matter, model accuracy can become reliant on the description of short- and long-range physical interactions. The latter terms can be difficult to incorporate into an MLIP framework. Recent research has produced numerous models with considerations for nonlocal electrostatic and dispersion interactions, leading to a large range of applications that can be addressed using MLIPs. In light of this, we present a Perspective focused on key methodologies and models being used where the presence of nonlocal physics and chemistry are crucial for describing system properties. The strategies covered include MLIPs augmented with dispersion corrections, electrostatics calculated with charges predicted from atomic environment descriptors, the use of self-consistency and…

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse intersystem crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here we compare the results of widely used DFT functionals, CAM-B3LYP, LC-ꞷPBE, LC-ꞷ*PBE, LC-ꞷ*HPBE, B3LYP, PBE0 and M06-2X against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled-Cluster (SCS-CC2) in fourteen known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm-Dancoff Approximation (TDA) together with the CAM-B3LYP, M06-2X and the two…

Ammonia is considered as one of the promising hydrogen carriers toward a sustainable world. Plasma assisted decomposition of NH 3 could provide cost- and energy-effective, low-temperature, on-demand (partial) cracking of NH 3 into H 2 . Here, we presented a temperature-dependent plasma-chemical kinetic study to investigate the role of both electron-induced reactions and thermally induced reactions on the decomposition of NH 3 . We employed a plasma-chemical kinetic model (KAUSTKin), developed a plasma-chemical reaction mechanism for the numerical analysis, and introduced a temperature-controlled dielectric barrier discharge reactor for the experimental investigation using 1 mol % NH 3 diluted in N 2 . As a result, we observed the plasma significantly lowered the cracking temperature and found that the plasma-chemical mechanism should be further improved to better predict the experiment. The commonly used rates for the key NH 3 pyrolysis reaction (NH 3 + M ↔ NH 2 + H + M) significantly overpredicted the recombination rate at temperatures below 600 K. Furthermore, the other identified…

, values extracted from the computed nonlinear optical (NLO) properties. Moreover, the reduced density gradient (RDG)-based noncovalent interactions (NCIs) were employed to characterize the strength and type of NBD-Si interactions. Furthermore, noncovalent interactions were identified and categorized using the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Ultimately, the combination of Hirshfeld surface analysis and DFT calculations was utilized to enhance the characterization and rationalization of these NCIs.

Despite the widespread popularity of scaled harmonic frequency calculations to predict experimental fundamental frequencies in chemistry, sparse benchmarking is available to guide users on the appropriate level of theory and basis set choices (model chemistry) or deep understanding of expected errors. An updated assessment of the best approach for scaling to minimize errors is also overdue. Here, we assess the performance of over 600 popular, contemporary, and robust model chemistries in the calculation of scaled harmonic frequencies, evaluating different scaling factor types and their implications in the scaled harmonic frequencies and model chemistry performance. We can summarize our results into three main findings: (1) Using model-chemistry-specific scaling factors optimized for three different frequency regions (low (<1,000 cm –1 ), mid (1,000–2,000 cm –1 ), and high (>2,000 cm –1 )) results in substantial improvements in the agreement between the scaled harmonic and experimental frequencies compared to other choices. (2) Larger basis sets and more robust levels of theory…

Collisional complexes, which are formed as intermediate states in molecular collisions, are typically short-lived and decay within picoseconds. However, in ultracold collisions involving bialkali molecules, complexes can live for milliseconds, completely changing the collision dynamics. This can lead to unexpected two-body loss in samples of nonreactive molecules. During the past decade, such "sticky" collisions have been a major hindrance in the preparation of dense and stable molecular samples, especially in the quantum-degenerate regime. Currently, the behavior of the complexes is not fully understood. For example, in some cases, their lifetime has been measured to be many orders of magnitude longer than recent models predict. This is not only an intriguing problem in itself but also practically relevant, since understanding molecular complexes may help to mitigate their detrimental effects. Here, we review the recent experimental and theoretical progress in this field. We treat the case of molecule-molecule as well as molecule-atom collisions.

Automation of rate-coefficient calculations for gas-phase organic species became possible in recent years and has transformed how we explore these complicated systems computationally. Kinetics workflow tools bring rigor and speed and eliminate a large fraction of manual labor and related error sources. In this paper we give an overview of this quickly evolving field and illustrate, through five detailed examples, the capabilities of our own automated tool, KinBot. We bring examples from combustion and atmospheric chemistry of C-, H-, O-, and N-atom-containing species that are relevant to molecular weight growth and autoxidation processes. The examples shed light on the capabilities of automation and also highlight particular challenges associated with the various chemical systems that need to be addressed in future work.

Basis sets are a crucial but often largely overlooked choice in setting up quantum chemistry calculations. The choice of the basis set can be critical in determining the accuracy and calculation time of your quantum chemistry calculations. Clear recommendations based on thorough benchmarking are essential but not readily available currently. This study investigates the relative quality of basis sets for general properties by benchmarking basis set performance for a diverse set of 139 reactions (from the diet-150-GMTKN55 data set). In our analysis, we find the distributions of errors are often significantly non-Gaussian, meaning that the joint consideration of median errors, mean absolute errors, and outlier statistics is helpful to provide a holistic understanding of basis set performance. Our direct comparison of performance between most modern basis sets provides quantitative evidence for basis set recommendations that broadly align with the established understanding of basis set experts and is evident in the design of modern basis sets. For example, while zeta is a good measure…

strategy. In this strategy, one essentially takes advantage of Fermi's golden rule (FGR) to evaluate rate constants at key points of the potential energy surfaces, a procedure that can be refined in a variety of ways. In this way, the radiative rate constant can be straightforwardly obtained by integrating the fluorescence line shape, itself determined from vibronic calculations. Likewise, FGR allows for a consistent calculation of the internal conversion (related to the non-adiabatic couplings) in the weak-coupling regime and intersystem crossing rates, therefore giving access to estimates of the emission yields when no complex photophysical phenomenon is at play. Beyond outlining the underlying theories, we summarize here the results of benchmarks performed for various types of rates, highlighting that both the quality of the vibronic calculations and the accuracy of the relative energies are crucial to reaching semiquantitative estimates. Finally, we illustrate the successes and challenges in determining the fluorescence quantum yields using a series of organic fluorophores.

Burgeoning developments in machine learning (ML) and its rapidly growing adaptations in chemistry are noteworthy. Motivated by the successful deployments of ML in the realm of molecular property prediction (MPP) and chemical reaction prediction (CRP), herein we highlight some of its most recent applications in predictive chemistry. We present a nonmathematical and concise overview of the progression of ML implementations, ranging from an ensemble-based random forest model to advanced graph neural network algorithms. Similarly, the prospects of various feature engineering and feature learning approaches that work in conjunction with ML models are described. Highly accurate predictions reported in MPP tasks (e.g., lipophilicity, solubility, distribution coefficient), using methods such as D-MPNN, MolCLR, SMILES-BERT, and MolBERT, offer promising avenues in molecular design and drug discovery. Whereas MPP pertains to a given molecule, ML applications in chemical reactions present a different level of challenge, primarily arising from the simultaneous involvement of multiple molecules…

The low reactivity of ammonia (NH 3 ) is the main barrier to applying neat NH 3 as fuel in technical applications, such as internal combustion engines and gas turbines. Introducing combustion promoters as additives in NH 3 -based fuel can be a feasible solution. In this work, the oxidation of ammonia by adding different reactivity promoters, i.e., hydrogen (H 2 ), methane (CH 4 ), and methanol (CH 3 OH), was investigated in a jet-stirred reactor (JSR) at temperatures between 700 and 1200 K and at a pressure of 1 bar. The effect of ozone (O 3 ) was also studied, starting from an extremely low temperature (450 K). Species mole fraction profiles as a function of the temperature were measured by molecular-beam mass spectrometry (MBMS). With the help of the promoters, NH 3 consumption can be triggered at lower temperatures than in the neat NH 3 case. CH 3 OH has the most prominent effect on enhancing the reactivity, followed by H 2 and CH 4 . Furthermore, two-stage NH 3 consumption was observed in NH 3 /CH 3 OH blends, whereas no such phenomenon was found by adding H 2 or CH 4 . The…

In this study, 550 C–F bond dissociation energies (BDEs) of a variety of per- and polyfluoroalkyl substances (PFASs) obtained from high-level DLPNO-CCSD(T)/CBS calculations were used to assess the accuracy of contemporary density functional theory (DFT) and semiempirical methods. DLPNO-CCSD(T)/CBS gas phase C–F BDEs fall between 404.9–550.7 kJ mol –1 and M06-2X and ωB97M-V in conjunction with the aug-cc-pVTZ basis set predicted BDEs closest to the benchmark level with a mean absolute deviation (MAD) of 7.3 and 8.3 kJ mol –1, respectively. It was observed that DFT prediction errors increase with the degree of fluorination and system size. As such, previous model chemistry recommendations based on smaller nonfluorinated systems may not be carried over to modeling the energetics of PFASs and related systems.

The current benchmark study is focused on determining the most precise theoretical method for optimizing the geometry of transition metal-dinitrogen complexes. To accomplish this goal, seven density functional (DF) methods from five distinct classes of density functional theory (DFT) have been selected, including B3LYP-D3(BJ), BP86-D3(BJ), PBE0-D3(BJ), ωB97X-D, M06, M06-L, and TPSSh-D3(BJ). These DFs will be utilized with the Karlsruhe basis set (def2-SVP). To carry out this benchmark study, a total of forty-two structurally diverse transition metal-dinitrogen compounds with experimentally known X-ray data have been selected from the Cambridge Crystallographic Data Centre (CCDC). Based on a comparison of the theoretical data with experimental values (X-ray) of the selected transition metal-dinitrogen compounds, statistical parameters such as root-mean-square deviation (RMSD) and N-N and M-N bond lengths are obtained to evaluate the performance of the seven chosen DFs. According to the obtained results, among all DFT methods used in the study, Minnesota functionals (M06 and M06-L)…

The outstanding capability of Frustrated Lewis Pair (FLP) catalysts to activate small molecules has gained significant attention in recent times. Reactivity of FLP is further extended toward the hydrogenation of various unsaturated species. Over the past decade, this unique catalysis concept has been successfully expanded to heterogeneous catalysis as well. The present review article gives a brief survey on several studies on this field. A thorough discussion on quantum chemical studies concerning the activation of H 2 is provided. The role of aromaticity and boron–ligand cooperation on the reactivity of FLP is discussed in the Review. How FLP can activate other small molecules by cooperative action of its Lewis centers is also discussed. Further, the discussion is shifted to the hydrogenation of various unsaturated species and the mechanism regarding this process. It also discusses the latest theoretical advancements in the application of FLP in heterogeneous catalysis across various domains, such as two-dimensional materials, functionalized surfaces, and metal oxides. A deeper…

Intramolecular hydrogen bonding (HB) is a complex phenomenon that extends beyond a simple valence event, affecting the core electrons of a molecule. Salicylic acid (SA) and its conformers provide an excellent model compound for studying intramolecular HB as the proton donor (H) and acceptor (O) can be toggled by rotating the C–O and C–C bonds to form up to seven potential conformers through various HB. In this study, we computationally investigated intramolecular interactions in SA conformers with and without such HB, by examining their calculated O 1s core electron-binding energy (CEBE) and 1 H NMR chemical shifts validated using recent measurements. The quantum mechanically stable SA conformers are fully defined by three rotatable bonds in the compound, which are abstracted as SA(η 1 η 2 η 3 ) digital structures, where η i = 0 if the η i angles match the most stable SA conformer (000) and η i = 1 otherwise. Our findings suggest that the stability is dominated by the appearance of the intergroup intramolecular HB of H p ···O (where O is in the carboxylic acid functional group and H…

We have developed a new method to accurately account for solvation effects in semiempirical quantum mechanics based on a polarizable continuum model (PCM). The extended conductor-like polarizable continuum model (CPCM-X) incorporates a computationally efficient domain decomposition conductor-like screening model (ddCOSMO) for extended tight binding (xTB) methods and uses a post-processing approach based on established solvation models, like the conductor-like screening model for real solvents (COSMO-RS) and the universal solvent model based on solute electron density (SMD). According to various benchmarks, the approach performs well across a broad range of systems and applications, including hydration free energies, non-aqueous solvation free energies, and large supramolecular association reactions of neutral and charged species. Our method for computing solvation free energies is much more accurate than the current methods in the xtb program package. It improves the accuracy of solvation free energies by up to 40% for larger supramolecular association reactions to match even the…

High Resolution Image Download MS PowerPoint Slide Nonadiabatic molecular dynamics offers a powerful tool for studying the photochemistry of molecular systems. Key to any nonadiabatic molecular dynamics simulation is the definition of its initial conditions (ICs), ideally representing the initial molecular quantum state of the system of interest. In this work, we provide a detailed analysis of how ICs may influence the calculation of experimental observables by focusing on the photochemistry of methylhydroperoxide (MHP), the simplest and most abundant organic peroxide in our atmosphere. We investigate the outcome of trajectory surface hopping simulations for distinct sets of ICs sampled from different approximate quantum distributions, namely harmonic Wigner functions and ab initio molecular dynamics using a quantum thermostat (QT). Calculating photoabsorption cross-sections, quantum yields, and translational kinetic energy maps from the results of these simulations reveals the significant effect of the ICs, in particular when low-frequency (∼ a few hundred cm –1 ) normal modes are…

Many recent research studies have reported indirect methods for the detection and quantification of OH radicals generated during photocatalysis. The short lifespan and high reactivity of these radicals make indirect detection using probes such as coumarin a more viable quantification method. Hydroxyl radical production is commonly monitored using fluorescence spectroscopy to determine the concentration of the compound 7-hydroxycoumarin, which is formed from hydroxyl radical attack on coumarin. There are, however, a number of additional hydroxylated coumarins generated during this process, which are less amenable to detection by fluorescence spectroscopy. Consequently, limitations and inaccuracies of this method have previously been reported in the literature. As an alternative approach to those previously reported, this work has developed an electrochemical screening method using coumarin as a OH radical trap, that is capable of in situ monitoring of not only 7-hydroxycoumarin, but all the main mono-hydroxylated products formed. As a result, this technique is a more representative…

Thermally activated delayed fluorescence (TADF) molecules are promising for realizing durable organic light-emitting diodes in all color regions. Fast reverse intersystem crossing (RISC) is a way of improving the device lifetime of TADF-based organic light-emitting diodes. To date, RISC rate constants (kRISC) of 10^8 s−1 have been reported for metal-free TADF molecules. Here, we report the heavy-atom effect on TADF and a molecular design for further promoting RISC. First, the RISC mechanism of a sulfur-containing TADF molecule (with kRISC of 10^8 s−1) was comprehensively investigated via density functional theory. The role of the heavy-atom effect on the rapid RISC process was clarified. Our calculations also predicted that much larger kRISC (>10^10 s−1) will be obtained for selenium- and tellurium-containing TADF molecules. However, a polonium-containing molecule promotes phosphorescence without exhibiting TADF, indicating that too strong heavy-atom effect is unfavorable for achieving both rapid RISC and efficient TADF.

Microdroplet chemistry has been an emerging new field for its large plethora of unique properties, among which an especially intriguing one is the strong oxidizing and reducing powers. The hydroxide ion in water microdroplets is considered to split into a hydroxyl radical and an electron at the air–water interface, and the former is responsible for the oxidizing capability while the latter is responsible for the reducing power, making a unity of opposites. However, to date there are only two examples showing that oxidation and reduction occur simultaneously to the same substrates, which might be a result of the redox properties of the substrate per se . In this study, we carefully chose a group of ο -quinone compounds as the substrates in water microdroplets and discovered that they can be both oxidized by the hydroxyl radical and reduced by the electron. These results keep pushing the limit of the unique redox properties of microdroplet chemistry.

High Resolution Image Download MS PowerPoint Slide In this work, five novel A-π-D-π-A type molecules D1–D5 were designed by adding unusual benzothiadiazole derivatives as π-spacer blocks to the efficient reference molecule DRCN5T for application as donor materials in organic solar cells (OSCs). Based on a density functional theory approach, a comprehensive theoretical study was performed with different functionals (B3LYP, B3LYP-GD3, B3LYP-GD3BJ, CAM-B3LYP, M06, M062X, and wB97XD) and with different solvent types (PCM and SMD) at the extended basis set 6-311+g(d,p) to evaluate the structural, optoelectronic, and intramolecular charge transfer properties of these molecules. The B3LYP-GD3BJ hybrid functional was used to optimize the studied molecules in CHCl 3 solution with the SMD model solvent as it provided the best results compared to experimental data. Transition density matrix maps were simulated to examine the hole–electron localization and the electronic excitation processes in the excited state, and photovoltaic parameters including open-circuit photovoltage and fill factor…

methods for the calculation of excited electronic states and electron-detached and -attached states. All ADC methods have been demonstrated to possess great potential for molecular applications, e.g., for the calculation of absorption or photoelectron spectra or electron attachment processes. ADC originates from Green's function or propagator theory; however, most recent ADC developments heavily rely on the intermediate state representation or effective Liouvillian formalisms, which comprise new ADC methods and computational schemes for high-order properties. The different approaches for the calculation of excitation energies, ionization potentials, and electron affinities are intimately related, and they provide a coherent description of these quantities at equivalent levels of theory and with comparable errors. Most quantum chemical program packages contain ADC methods; however, the most complete ADC suite of methods can be found in the recent release of Q-Chem.

This Perspective attempts to shed light on developments in the theoretical and experimental study of molecular anions highlighting more recent workers in the field. The species I discuss include (i) valence-bound (singly and multiply charged) anions including atmospheric, catalytic, superhalogen, interfacial, and more; (ii) dipole- and correlation-bound anions including their role as doorways to other states and their appearance "in space", and (iii) metastable anions focusing on tools needed for their theoretical treatment. I also briefly discuss angular distributions of photodetached electrons and their growing utilization in experiments and theory. A recurring theme is the dependence of electron binding energies (EBEs) on the surrounding environment. Some anions that are nonexistent as isolated species evolve to be stable but with small EBEs when weakly solvated (e.g., as in a cluster or at an air-solvent interface). Others existing in isolation only as metastable species become stable when the underlying molecular framework contains one or more positively charged group (e.g.,…

The reaction NH 3 + NH 2 ⇄ N 2 H 3 + H 2 (R1) has been identified as a key step to explain experimental results for pyrolysis and oxidation of ammonia. However, no direct experimental or theoretical evidence for the reaction has been reported. In the present work, the reaction was studied by ab initio theory and by reinterpretation of experimental data. We could not locate a transition state for R1 occurring as a direct process, but alternative mechanisms yielded an upper bound to k 1 of 1.5 × 10 13 exp(−58.9 kcal mol –1 / RT ) cm 3 mol –1 s –1 over 1000–2500 K, several orders of magnitude lower than values applied in modeling. Consistent with the theoretical work, re-evaluation of NH 3 pyrolysis data supported a very low value of k 1 . However, this finding opens up a novel unresolved issue. Current kinetic models cannot capture the NH 3 oxidation behavior in a number of laminar flow reactor and jet-stirred reactor experiments without adopting an improbably high value for k 1 . Important oxidation steps might be underestimated or missing from mechanisms.

Organic nitrates (ONs) can impact spatial distribution of reactive nitrogen species and ozone formation in the atmosphere. While photolysis of ONs is known to result in the release of NO 2 back to the atmosphere, the photolysis rate constants and mechanisms of monoterpene-derived ONs (MT-ONs) have not been well constrained. We investigated the gas-phase photolysis of three synthetic ONs derived from α-pinene, β-pinene, and d -limonene through chamber experiments. The measured photolysis rate constants ranged from (0.55 ± 0.10) × 10 –5 to (2.3 ± 0.80) × 10 –5 s –1 under chamber black lights. When extrapolated to solar spectral photon flux at a solar zenith angle of 28.14° in summer, the photolysis rate constants were in the range of (4.1 ± 1.4) × 10 –5 to (14 ± 6.7) × 10 –5 s –1 (corresponding to lifetimes of 2.0 ± 0.96 to 6.8 ± 2.4 h) and (1.7 ± 0.60) × 10 –5 to (8.3 ± 4.0) ×10 –5 s –1 (3.3 ± 1.6 to 17 ± 6.0 h lifetimes) by using wavelength-dependent and average quantum yields, respectively. Photolysis mechanisms were proposed based on major products detected during photolysis. A…

While density-functional theory (DFT) remains one of the most widely used tools in computational chemistry, most functionals fail to properly account for the effects of London dispersion. Hence, there are many popular post-self-consistent methods to add a dispersion correction to the DFT energy. Until now, the most popular methods have never been compared on equal footing due to not being implemented in the same electronic structure packages. In this work, we performed a large-scale benchmarking study, directly comparing the accuracy of the exchange-hole dipole moment (XDM), D3BJ, D4, TS, MBD, and MBD-NL dispersion models when applied to the recent DES15K database of nearly 15,000 molecular complexes at both expanded and compressed geometries. Our study showed similarly good performance for all dispersion methods (except TS) when applied to neutral complexes. However, they all performed worse for ionic complexes, particularly those involving dications of alkaline earth metals, due to systematic overbinding by the base PBE0 density functional. Investigation of the largest outliers…

Cavity quantum electrodynamics (QED) generalizations of time-dependent (TD) density functional theory (DFT) and equation-of-motion (EOM) coupled-cluster (CC) theory are used to model small molecules strongly coupled to optical cavity modes. We consider two types of calculations. In the first approach (termed "relaxed"), we use a coherent-state-transformed Hamiltonian within the ground- and excited-state portions of the calculations, and cavity-induced orbital relaxation effects are included at the mean-field level. This procedure guarantees that the energy is origin-invariant in post-self-consistent-field calculations. In the second approach (termed "unrelaxed"), we ignore the coherent-state transformation and the associated orbital relaxation effects. In this case, ground-state unrelaxed QED-CC calculations pick up a modest origin dependence but otherwise reproduce relaxed QED-CC results within the coherent-state basis. On the other hand, a severe origin dependence manifests in ground-state unrelaxed QED mean-field energies. For excitation energies computed at experimentally…

High Resolution Image Download MS PowerPoint Slide The chemical shift (CS) values obtained by 1 H NMR spectroscopy for the hydrogen atoms of a tetradentate N 2 O 2 -substituted Salphen ligand (H 2 L1 ) are differently shifted in its complexes of nickel(II), palladium(II), platinum(II), and zinc(II), all bearing the same charge on the metal ions. To rationalize the observed trends, DFT calculations have been performed in the implicit d 6 -DMSO solvent in terms of the electronic effects induced by the metal ion and of the nature and strength of the metal-N and metal-O bonds. Overall, the results obtained point out that, in the complexes involving group 10 elements, the CS values show the greater shift when considering the two hydrogen atoms at a shorter distance from the coordinated metal center and follow the decreasing metal charge in the order Ni > Pd > Pt. This trend suggests a more covalent character of the ligand–metal bonds with the increase of the metal atomic number. Furthermore, a slightly poorer agreement between experimental and calculated data is observed in the presence…

(6-31G) and the avoided crossing in LiF (6-31G), revealing the severity of root flipping and demonstrating that state-specific solutions can behave quasi-diabatically or adiabatically. These results elucidate the complexity of the CASSCF energy landscape, highlighting the advantages and challenges of practical state-specific calculations.

Methane pyrolysis is a very attractive and climate-friendly process for hydrogen production and the sequestration of carbon as solid material. The formation of soot particles in methane pyrolysis reactors needs to be understood for technology scale-up calling for appropriate soot growth models. A monodisperse model is coupled with a plug flow reactor model and elementary-step reaction mechanisms to numerically simulate processes in methane pyrolysis reactors, namely, the chemical conversion of methane to hydrogen, formation of C-C coupling products and polycyclic aromatic hydrocarbons, and growth of soot particles. The soot growth model accounts for the effective structure of the aggregates by calculating the coagulation frequency from the free-molecular regime to the continuum regime. It predicts the soot mass, particle number, area, and volume concentration, along with the particle size distribution. For comparison, experiments on methane pyrolysis are carried out at different temperatures and collected soot samples are characterized using Raman spectroscopy, transmission electron…

It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce Δ H f (0 K) values with 2σ uncertainties of 0.2–0.5 kcal mol –1 . This set includes the alkanes, hydroperoxides, and alkyl, peroxy, and hydroperoxyalkyl radicals for 17 representative hydrocarbon fuels containing up to 10 heavy atoms with various degrees of branching in the alkane backbone. The CBH-ANL approach, automated in the QTC and AutoMech software suites, builds balanced chemical equations for the calculation of Δ H f (0 K), in which the reference species may be up to five heavy atoms. The high-level ANL0 and ANL1 reference Δ H f (0 K) values are further refined for even the largest of these reference species with a novel laddering approach. We perform a comprehensive quantification of the uncertainties for both the individual reference…

Quantum simulations of the hydroxide anion and hydroxyl radical are reported, employing variational quantum algorithms for near-term quantum devices. The energy of each species is calculated along the dissociation curve, to obtain information about the stability of the molecular species being investigated. It is shown that simulations restricted to valence spaces incorrectly predict the hydroxyl radical to be more stable than the hydroxide anion. Inclusion of dynamical electron correlation from nonvalence orbitals is demonstrated, through the integration of the variational quantum eigensolver and quantum subspace expansion methods in the workflow of N -electron valence perturbation theory, and shown to correctly predict the hydroxide anion to be more stable than the hydroxyl radical, provided that basis sets with diffuse orbitals are also employed. Finally, we calculate the electron affinity of the hydroxyl radical using an aug-cc-pVQZ basis on IBM’s quantum devices.

A new approach to computation at affordable cost of accurate geometrical structures and rotational constants for medium-sized molecules in the gas phase is further improved and applied to a large panel of interstellar complex organic molecules. The most distinctive feature of the new model is the effective inclusion of core-valence correlation and vibrational averaging effects in the framework of density functional theory (DFT). In particular, a double-hybrid functional in conjunction with a quadruple-ζ valence/triple-ζ polarization basis set is employed for geometry optimizations, whereas a cheaper hybrid functional in conjunction with a split-valence basis set is used for the evaluation of vibrational corrections. A thorough benchmark based on a wide range of prototypical systems shows that the new scheme approaches the accuracy of state-of-the-art wave function methods with the computational cost of the standard methods (DFT or MP2) routinely employed in the interpretation of microwave spectra. Since the whole computational workflow involves the postprocessing of the output of…

A computational design of linearly extended multiple resonance (MR)-type BN molecules based on DABNA-1 is proposed herein in the quest to find potential candidates that exhibit a negative singlet-triplet gap (ΔEST) and a large oscillator strength. The impact of a proper account of electron correlation in the lowest singlet and triplet excited states is systematically investigated by using double-hybrid functionals within the TD-DFT framework as well as wavefunction-based methods (EOM-CCSD and SCS-CC2) since this contribution plays an essential role in driving the magnitude of the ΔEST in MR-TADF and inverted singlet-triplet gap. Our results point out to a gradual reduction of the ΔEST gap with respect to the increasing sum of the number of B and N atoms, reaching negative ΔEST values for some molecules as a function of their size. The double hybrid functionals reproduce the gap with only slight deviation compared to available experimental data for DABNA-1, ν-DABNA, and mDBCz and nicely agree with high-level quantum mechanical methods (e.g., EOM-CCSD and SCS-CC2). Larger oscillator…

Since the structures of crystals/molecules are often non-Euclidean data in real space, graph neural networks (GNNs) are regarded as the most prospective approach for their capacity to represent materials by graph-based inputs and have emerged as an efficient and powerful tool in accelerating the discovery of new materials. Here, we propose a self-learning-input GNN framework, named self-learning-input GNN (SLI-GNN), to uniformly predict the properties for both crystals and molecules, in which we design a dynamic embedding layer to self-update the input features along with the iteration of the neural network and introduce the Infomax mechanism to maximize the average mutual information between the local features and the global features. Our SLI-GNN can reach ideal prediction accuracy with fewer inputs and more message passing neural network (MPNN) layers. The model evaluations on the Materials Project dataset and QM9 dataset verify that the overall performance of our SLI-GNN is comparable to that of other previously reported GNNs. Thus, our SLI-GNN framework presents excellent…

The formation of molecular clusters and secondary aerosols in the atmosphere has a significant impact on the climate. Studies typically focus on the new particle formation (NPF) of sulfuric acid (SA) with a single base molecule (e.g., dimethylamine or ammonia). In this work, we examine the combinations and synergy of several bases. Specifically, we used computational quantum chemistry to perform configurational sampling (CS) of (SA) 0–4 (base) 0–4 clusters with five different types of bases: ammonia (AM), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA). Overall, we studied 316 different clusters. We used a traditional multilevel funnelling sampling approach augmented by a machine-learning (ML) step. The ML made the CS of these clusters possible by significantly enhancing the speed and quality of the search for the lowest free energy configurations. Subsequently, the cluster thermodynamics properties were evaluated at the DLPNO–CCSD(T 0 )/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level of theory. The calculated binding free energies were used to…

Fragmentation and embedding schemes are of great importance when applying quantum-chemical calculations to more complex and attractive targets. The divide-and-conquer (DC)-based quantum-chemical model is a fragmentation scheme that can be connected to embedding schemes. This feature article explains several DC-based schemes developed by the authors over the last two decades, which was inspired by the pioneering study of DC self-consistent field (SCF) method by Yang and Lee ( J. Chem. Phys . 1995, 103, 5674–5678). First, the theoretical aspects of the DC-based SCF, electron correlation, excited-state, and nuclear orbital methods are described, followed by the two-component relativistic theory, quantum-mechanical molecular dynamics simulation, and the introduction of three programs, including DC-based schemes. Illustrative applications confirmed the accuracy and feasibility of the DC-based schemes.

Recent modeling studies of ammonia oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies among the existing literature mechanisms. In this study, high-level theoretical kinetics predictions have been obtained for reactions on the NH 2 O potential energy surface, including the NH 2 + O, HNO + H, and NH + OH reactions. These reactions have previously been highlighted as important reactions in NH 3 oxidation with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations, including large basis sets and high-level corrections to yield high-accuracy (∼0.2 kcal/mol 2σ uncertainty) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature- and pressure-dependent kinetics. For radical–radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing…

High Resolution Image Download MS PowerPoint Slide The nuclear magnetic resonance (NMR) chemical shift tensor is a highly sensitive probe of the electronic structure of an atom and furthermore its local structure. Recently, machine learning has been applied to NMR in the prediction of isotropic chemical shifts from a structure. Current machine learning models, however, often ignore the full chemical shift tensor for the easier-to-predict isotropic chemical shift, effectively ignoring a multitude of structural information available in the NMR chemical shift tensor. Here we use an equivariant graph neural network (GNN) to predict full 29 Si chemical shift tensors in silicate materials. The equivariant GNN model predicts full tensors to a mean absolute error of 1.05 ppm and is able to accurately determine the magnitude, anisotropy, and tensor orientation in a diverse set of silicon oxide local structures. When compared with other models, the equivariant GNN model outperforms the state-of-the-art machine learning models by 53%. The equivariant GNN model also outperforms historic…

We present a high-performance evaluation method for 4-center 2-particle integrals over Gaussian atomic orbitals with high angular momenta ( l ≥ 4) and arbitrary contraction degrees on graphical processing units (GPUs) and other accelerators. The implementation uses the matrix form of McMurchie–Davidson recurrences. Evaluation of the four-center integrals over four l = 6 (i) Gaussian AOs in double precision (FP64) on an NVIDIA V100 GPU outperforms the reference implementation of the Obara-Saika recurrences (Libint) running on a single Intel Xeon core by more than a factor of 1000, easily exceeding the 73:1 ratio of the respective hardware peak FLOP rates while reaching almost 50% of the V100 peak. The approach can be extended to support AOs with even higher angular momenta; for lower angular momenta ( l ≤ 3), additional improvements will be reported elsewhere. The implementation is part of an open-source LibintX library freely available at github.com:ValeevGroup/LibintX .

The SE100 database collecting accurate equilibrium geometries of medium size molecules obtained by the semiexperimental (SE) approach has been extended to species containing Br and I atoms. This has allowed the determination of accurate linear regressions between DFT and SE values for all the main bonds and angles involving H, B, C, N, O, F, P, S, Cl, Br, and I atoms. An improved Nano-LEGO tool has been developed, which is based on suitable hybrid and double hybrid functionals and combines in a fully coherent way the templating molecule and linear regression approaches. A number of case studies show that the new Nano LEGO tool provides geometrical parameters on par with state-of-the-art composite wave function methods, but can be routinely applied to medium- to large-size molecules. The accuracy reached for structural parameters is mirrored on rotational constants that can be predicted with an average error within 0.2%.

Ab initio predictions of chemical shifts and electric field gradient (EFG) tensor components are frequently used to help interpret solid-state nuclear magnetic resonance (NMR) experiments. Typically, these predictions employ density functional theory (DFT) with generalized gradient approximation (GGA) functionals, though hybrid functionals have been shown to improve accuracy relative to experiment. Here, the performance of a dozen models beyond the GGA approximation are examined for the prediction of solid-state NMR observables, including meta-GGA, hybrid, and double-hybrid density functionals and second-order Møller–Plesset perturbation theory (MP2). These models are tested on organic molecular crystal data sets containing 169 experimental 13 C and 15 N chemical shifts and 114 17 O and 14 N EFG tensor components. To make these calculations affordable, gauge-including projector augmented wave (GIPAW) Perdew–Burke–Ernzerhof (PBE) calculations with periodic boundary conditions are combined with a local intramolecular correction computed at the higher level of theory. Within the…

The intramolecular hydrogen-shift rate coefficient of the CH 3 SCH 2 O 2 (methylthiomethylperoxy, MSP) radical, a product formed in the oxidation of dimethyl sulfide (DMS), was measured using a pulsed laser photolysis flow tube reactor coupled to a high-resolution time-of-flight chemical ionization mass spectrometer that measured the formation of the DMS degradation end product HOOCH 2 SCHO (hydroperoxymethyl thioformate). Measurements performed over the temperature range of 314–433 K yielded a hydrogen-shift rate coefficient of k 1 ( T ) = (2.39 ± 0.7) × 10 9 exp(−(7278 ± 99)/ T ) s –1 Arrhenius expression and a value extrapolated to 298 K of 0.06 s –1 . The potential energy surface and the rate coefficient have also been theoretically investigated using density functional theory at the M06-2X/aug-cc-pVTZ level combined with approximate CCSD(T)/CBS energies yielding k 1 (273–433 K) = 2.4 × 10 11 × exp(−8782/ T ) s –1 and k 1 (298 K) = 0.037 s –1 in fair agreement with the experimental results. Present results are compared with the previously reported values of k 1 (293–298 K).

X-ray photoemission spectroscopy (XPS) provides direct information on atomic composition and stoichiometry by measuring core–electron binding energies. Moreover, from the shift of the binding energy, the so-called chemical shift, the precise chemical type of bonds can be inferred, which brings additional information on the local structure. In this work, we present a theoretical study of the chemical shift first by comparing different theories, from Hartree–Fock and density functional theory to many-body perturbation theory approaches like the GW approximation and its static version (COHSEX). The accuracy of each theory is assessed with respect to a carbon 1 s chemical shift experimental benchmark measured on a set of gas-phase molecules. More importantly, by decomposing the chemical shift into different contributions according to terms in the total Hamiltonian, classical electrostatics is identified as the major contributor to the chemical shift, one order of magnitude larger than the correlation.

We re-examined the existence of planar tetracoordinate F (ptF) atoms, which was proposed recently by using high-level ab initio methods such as coupled-cluster singles and doubles with perturbative triples (CCSD(T)) with large basis sets. Our calculations indicate that the planar structures of FIn 4 + ( D 4h ), FTl 4 + ( D 4h ), FGaIn 3 + ( C 2V ), FIn 2 Tl 2 + ( D 2h ), FIn 3 Tl + ( C 2V ), and FInTl 3 + ( C 2V ) are not the minimum energy states; by contrast, they are transition states. Density functional theory calculations overestimate the size of the cavity formed by the four peripheral atoms, leading to erroneous conclusions regarding the existence of ptF atoms. Our analysis suggests that the preference for non-planar structures in the six cations studied is not due to the pseudo Jahn–Teller effect. Additionally, spin–orbit coupling does not alter the main conclusion that the ptF atom does not exist. If sufficiently large cavity formation by group 13 elements to accommodate the central F – ion is guaranteed, then the existence of ptF atoms is plausible.

Different machine learning (ML) models are proposed in the present work to predict density functional theory-quality barrier heights (BHs) from semiempirical quantum mechanical (SQM) calculations. The ML models include a multitask deep neural network, gradient-boosted trees by means of the XGBoost interface, and Gaussian process regression. The obtained mean absolute errors are similar to those of previous models considering the same number of data points. The ML corrections proposed in this paper could be useful for rapid screening of the large reaction networks that appear in combustion chemistry or in astrochemistry. Finally, our results show that 70% of the features with the highest impact on model output are bespoke predictors. This custom-made set of predictors could be employed by future Δ-ML models to improve the quantitative prediction of other reaction properties.

A new detailed chemical kinetic mechanism is presented for small fluorinated hydrocarbons. Ab initio electronic structure theory is used to provide heats of formation with subchemical accuracy. The ANL0 method is extended to include fluorine. The resulting heats of formation at 0 K are in excellent agreement with 36 benchmark species in the Active Thermochemical Tables, with a mean error of μ = −0.02 kJ/mol and a standard deviation of σ = 0.91 kJ/mol. The thermophysical properties for 92 small-molecule H/C/O/F species are computed. The rate coefficients for 40+ H-abstraction reactions involving H, O, F, OH, OF, HO 2, and various methyl radicals with CH 4, CH 3 F, CH 2 F 2, CHF 3, CH 2 O, and CHFO are discussed. The computed rate constants are in excellent agreement with the available literature. Additionally, 30+ rate constants are provided for F abstraction, which are several orders of magnitude smaller than H abstraction. The thermophysical properties and rate constants are provided in a mechanism. This mechanism is the first in a series of theory-based investigations into the…

Empirical substituent constants, such as the Hammett parameters, have found important utility in organic and other areas of chemistry. They are useful both in predicting the impact of substitutions on chemical processes and in rationalizing after-the-fact observations on chemical bonding and reactivity. We assess the impact of substitutions on monoiodinated benzene rings and find that the modifications that substituents induce on the electrostatic potentials at the sigma hole on the terminal I center correlate strongly with established trends of common substituents. As an alternative to the experimental procedures involved in obtaining empirically based substituent constants, the computationally determined constants based on induced electrostatic potentials offer a model for quantifying the influence of mono- and polyatomic, neutral, and ionic substituents on their compounds. A partitioning scheme is proposed that allows us to discretely separate σ and π contributions to generate quantitative measures of substituent effects.

This work compares eight classical H 2 molecular models in the gas phase taken from the existing literature. All models are based on Lennard-Jones (LJ) 12-6 terms for the van der Waals interactions and hence easier to transfer to multiphase molecular simulations than more sophisticated potentials. The H 2 potentials tested include one-site, two-site, three-site, and five-site models, with the sites being either the H atoms, the center-of-mass of the H 2 molecule, or massless sites. For the multisite models, high-frequency H–H stretching modes can lead to poor equipartition of the kinetic energy, and the timestep for molecular dynamics (MD) simulations should be reduced to maintain a stable numerical integration of the equations of motion. As such, only those models with rigid bonds are considered. In the present case, 600 MD simulations of H 2 gas were carried out over a large range of temperatures (−50 to +90 °C) and at densities corresponding to a pressure range of 50 to 2000 bar, which include the operating conditions of on-board storage tanks in hydrogen-fueled vehicles. Most of…