Complete Basis Research Articles

Hypergraphs in LHC phenomenology — the next frontier of IRC-safe feature extraction

In this study, we critically evaluate the approximation capabilities of existing infra-red and collinear (IRC) safe feature extraction algorithms, namely Energy Flow Networks (EFNs) and Energy-weighted Message Passing Networks (EMPNs). Our analysis reveals that these algorithms fall short in extracting features from any N-point correlation that isn’t a power of two, based on the complete basis of IRC safe observables, specifically C-correlators. To address this limitation, we introduce the Hypergraph Energy-weighted Message Passing Networks (H-EMPNs), designed to capture any N-point correlation among particles efficiently. Using the case study of top vs. QCD jets, which holds significant information in its 3-point correlations, we demonstrate that H-EMPNs targeting up to N=3 correlations exhibit superior performance compared to EMPNs focusing on up to N=4 correlations within jet constituents.

High Accuracy Ab Initio Potential Energy Curves and Dipole Moment Functions for the X1Σ+ and a3Π Spin States of the CF+ Diatomic Molecule.

Potential energy curves and dipole moment functions constructed using high-accuracy ab initio methods allow for an in-depth examination of the electronic structure of diatomic molecules. Ab initio computations serve as a valuable complement to experimental data, offering insights into the nature of short-lived molecules such as those encountered within the interstellar medium (ISM). While laboratory experiments provide critical groundwork, the ISM's conditions often permit longer lifetimes for lower stability molecules, enabling unique observations. The CF+ diatomic molecule is one such molecule that has been observed spectroscopically in the ISM. Previous experimental and theoretical work have examined different spectroscopic aspects of the CF+ molecule, but the development of newer, more complete potential energy curves and dipole moment functions allows for even greater insight. We constructed both potential energy curves and dipole moment functions for the ground X1Σ+ and first excited a3Π states of CF+ for both the 12C and 13C isotopologues. The potential energy curves were constructed using coupled cluster with single, double, and perturbative triple excitations (CCSD(T)) at the complete basis set limit with corrections from full triple, quadruple, quintuple, and hextuple excitations within a finite-basis coupled cluster wave function as well as corrections from full configuration interaction and relativistic effects. Rovibrational wave functions were calculated using a vibrational Hamiltonian matrix, which moves beyond the harmonic oscillator approximation. The equilibrium bond length, vibrational constant, and rotational constant were reproduced to within 0.00013 Å, 0.28 cm-1, and 0.00045 cm-1, respectively, of experimental values. Experimental transition energies from rovibrational spectra were reproduced with an error of no larger than 0.63 cm-1. The triplet excited state (a3Π) was found to have a longer equilibrium bond length at 1.21069 Å, a vibrational constant of 1611.29 cm-1, and a rotational constant of 1.56376 cm-1. Rovibrational line lists for the 12C and 13C isotopologues for both the X1Σ+ and the excited a3Π states were generated.

Theoretical kinetic study of key reactions between ammonia and fuel molecules, part I: Hydrogen atom abstraction from alkanes by ṄH2 radical

Cross reactions between ṄH2 radical and fuel molecules are essential in determining the reactivity for ammonia/fuel blends. A systematic theoretical chemical kinetic investigation of hydrogen atom abstraction by ṄH2 radical from C1–C6 alkanes, n-heptane, and isooctane has been performed in this study. The geometry optimization, frequency, and zero-point energy calculations for all species related to the title reactions were calculated at the M06-2X/6-311++G(d,p) level of theory. One-dimensional hindered rotor treatment has also been performed at the same level of theory to obtain the potential energy surface for the low frequency torsional modes. Single-point energy was obtained at the QCISD(T)/cc-pVDZ, QCISD(T)/cc-pVTZ, MP2/cc-pVDZ, MP2/cc-pVTZ and MP2/cc-pVQZ levels of theory and then extrapolated to the complete basis set. Benchmark calculations for single point energy have also been carried out at the CCSD(T)-F12/cc-pVTZ, CCSD(T)-F12/cc-pVQZ, CCSD(T)-F12/aug-cc-pVTZ and CCSD(T)-F12/aug-cc-pVQZ levels of theory based on the geometries obtained at the CCSD(T)/cc-pVDZ level of theory for the reaction systems of methane + ṄH2 and ethane + ṄH2. The rate constants of 41 reactions in the temperature range 298.15–2000 K were calculated by using the Master Equation System Solver (MESS) with conventional transition state theory. Good agreement has been gained between our calculated results and the available theoretical and experimental data in the literature. Rate rules for different reaction sites have also been derived, and the average rate constants for primary, secondary, and tertiary sites were also reported on a per hydrogen atom basis. The impact of calculation data for the ammonia/alkane blends model has also been investigated. The calculated rate constants are valuable for the combustion kinetic model development for ammonia blending fuels.

Non-collinear magnetic atomic cluster expansion for iron

The Atomic Cluster Expansion (ACE) provides a formally complete basis for the local atomic environment. ACE is not limited to representing energies as a function of atomic positions and chemical species, but can be generalized to vectorial or tensorial properties and to incorporate further degrees of freedom (DOF). This is crucial for magnetic materials with potential energy surfaces that depend on atomic positions and atomic magnetic moments simultaneously. In this work, we employ the ACE formalism to develop a non-collinear magnetic ACE parametrization for the prototypical magnetic element Fe. The model is trained on a broad range of collinear and non-collinear magnetic structures calculated using spin density functional theory. We demonstrate that the non-collinear magnetic ACE is able to reproduce not only ground state properties of various magnetic phases of Fe but also the magnetic and lattice excitations that are essential for a correct description of finite temperature behavior and properties of crystal defects.

Exploring the Tl H potential energy surface: A comparative analysis with group 13 systems and experiment.

Thallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet Tl H potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug-cc-pwCVQZ-PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug-cc-pwCVTZ-PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple-zeta cardinality (aug-cc-pwCV5Z-PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero-point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 M H (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

Developing correlation-consistent numeric atom-centered orbital basis sets for krypton: Applications in RPA-based correlated calculations.

Localized atomic orbitals are the preferred basis set choice for large-scale explicit correlated calculations, and high-quality hierarchical correlation-consistent basis sets are a prerequisite for correlated methods to deliver numerically reliable results. At present, numeric atom-centered orbital (NAO) basis sets with valence correlation consistency (VCC), designated as NAO-VCC-nZ, are only available for light elements from hydrogen (H) to argon (Ar) [Zhang et al., New J. Phys. 15, 123033 (2013)]. In this work, we extend this series by developing NAO-VCC-nZ basis sets for krypton (Kr), a prototypical element in the fourth row of the periodic table. We demonstrate that NAO-VCC-nZ basis sets facilitate the convergence of electronic total-energy calculations using the Random Phase Approximation (RPA), which can be used together with a two-point extrapolation scheme to approach the complete basis set limit. Notably, the Basis Set Superposition Error (BSSE) associated with the newly generated NAO basis sets is minimal, making them suitable for applications where BSSE correction is either cumbersome or impractical to do. After confirming the reliability of NAO basis sets for Kr, we proceed to calculate the Helmholtz free energy for Kr crystal at the theoretical level of RPA plus renormalized single excitation correction. From this, we derive the pressure-volume (P-V) diagram, which shows excellent agreement with the latest experimental data. Our work demonstrates the capability of correlation-consistent NAO basis sets for heavy elements, paving the way toward numerically reliable correlated calculations for bulk materials.

Capturing the electron-electron cusp with the coupling-constant averaged exchange-correlation hole: A case study for Hooke's atoms.

In density-functional theory, the exchange-correlation (XC) energy can be defined exactly through the coupling-constant (λ) averaged XC hole n̄xc(r,r'), representing the probability depletion of finding an electron at r' due to an electron at r. Accurate knowledge of n̄xc(r,r') has been crucial for developing XC energy density-functional approximations and understanding their performance for molecules and materials. However, there are very few systems for which accurate XC holes have been calculated since this requires evaluating the one- and two-particle reduced density matrices for a reference wave function over a range of λ while the electron density remains fixed at the physical (λ = 1) density. Although the coupled-cluster singles and doubles (CCSD) method can yield exact results for a two-electron system in the complete basis set limit, it cannot capture the electron-electron cusp using finite basis sets. Focusing on Hooke's atom as a two-electron model system for which certain analytic solutions are known, we examine the effect of this cusp error on the XC hole calculated using CCSD. The Lieb functional is calculated at a range of coupling constants to determine the λ-integrated XC hole. Our results indicate that, for Hooke's atoms, the error introduced by the description of the electron-electron cusp using Gaussian basis sets at the CCSD level is negligible compared to the basis set incompleteness error. The system-, angle-, and coupling-constant-averaged XC holes are also calculated and provide a benchmark against which the Perdew-Burke-Ernzerhof and local density approximation XC hole models are assessed.

Reliable Dimerization Energies for Modeling of Supramolecular Junctions.

Accurate estimates of intermolecular interaction energy, ΔE, are crucial for modeling the properties of organic electronic materials and many other systems. For a diverse set of 50 dimers comprising up to 50 atoms (Set50-50, with 7 of its members being models of single-stacking junctions), benchmark ΔE data were compiled. They were obtained by the focal-point strategy, which involves computations using the canonical variant of the coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] performed while applying a large basis set, along with extrapolations of the respective energy components to the complete basis set (CBS) limit. The resulting ΔE data were used to gauge the performance for the Set50-50 of several density-functional theory (DFT)-based approaches, and of one of the localized variants of the CCSD(T) method. This evaluation revealed that (1) the proposed "silver standard" approach, which employs the localized CCSD(T) method and CBS extrapolations, can be expected to provide accuracy better than two kJ/mol for absolute values of ΔE, and (2) from among the DFT techniques, computationally by far the cheapest approach (termed "ωB97X-3c/vDZP" by its authors) performed remarkably well. These findings are directly applicable in cost-effective yet reliable searches of the potential energy surfaces of noncovalent complexes.

Systematic analysis of electronic barrier heights and widths for concerted proton transfer in cyclic hydrogen bonded clusters: (HF)n, (HCl)n and (H2O)n where n = 3, 4, 5.

The MP2 and CCSD(T) methods are paired with correlation consistent basis sets as large as aug-cc-pVQZ to optimize the structures of the cyclic minima for (HF)n, (HCl)n and (H2O)n where n = 3-5, as well as the corresponding transition states (TSs) for concerted proton transfer (CPT). MP2 and CCSD(T) harmonic vibrational frequencies confirm the nature of each minimum and TS. Both conventional and explicitly correlated CCSD(T) computations are employed to assess the electronic dissociation energies and barrier heights for CPT near the complete basis (CBS) limit for all 9 clusters. Results for (HF)n are consistent with prior studies identifying Cnh and Dnh point group symmetry for the minima and TSs, respectively. Our computations also confirm that CPT proceeds through Cs TS structures for the C1 minima of (H2O)3 and (H2O)5, whereas the process goes through a TS with D2d symmetry for the S4 global minimum of (H2O)4. This work corroborates earlier findings that the minima for (HCl)3, (HCl)4 and (HCl)5 have C3h, S4 and C1 point group symmetry, respectively, and that the Cnh structures are not minima for n = 4 and 5. Moreover, our computations show the TSs for CPT in (HCl)3, (HCl)4 and (HCl)5 have D3h, D2d, and C2 point group symmetry, respectively. At the CCSD(T) CBS limit, (HF)4 and (HF)5 have the smallest electronic barrier heights for CPT (≈15 kcal mol-1 for both), followed by the HF trimer (≈21 kcal mol-1). The barriers are appreciably higher for the other clusters (around 27 kcal mol-1 for (H2O)4 and (HCl)3; roughly 30 kcal mol-1 for (H2O)3, (H2O)5 and (HCl)4; up to 38 kcal mol-1 for (HCl)5). At the CBS limit, MP2 significantly underestimates the CCSD(T) barrier heights (e.g., by ca. 2, 4 and 7 kcal mol-1 for the pentamers of HF, H2O and HCl, respectively), whereas CCSD overestimates these barriers by roughly the same magnitude. Scaling the barrier heights and dissociation energies by the number of fragments in the cluster reveals strong linear relationships between the two quantities and with the magnitudes of the imaginary vibrational frequency for the TSs.

Evaluation of surface roughness, wettability and adhesion of multispecies biofilm on 3D-printed resins for the base and teeth of complete dentures.

This study evaluated the surface roughness, wettability and adhesion of multispecies biofilms (Candida albicans, Staphylococcus aureus and Streptococcus mutans) on 3D-printed resins for complete denture bases and teeth compared to conventional resins (heat-polymerized acrylic resin; artificial pre-fabricated teeth). Circular specimens (n=39; 6.0 mm Ø × 2.0 mm) of each group were subjected to roughness (n=30), wettability (n=30) and biofilm adhesion (n=9) tests. Three roughness measurements were taken by laser confocal microscopy and a mean value was calculated. Wettability was evaluated by the contact angle of sessile drop method, considering the mean of the three evaluations per specimen. In parallel, microorganism adhesion to resin surfaces was evaluated using a multispecies biofilm model. Microbial load was evaluated by determining the number of Colony Forming Units (CFU/mL) and by scanning electron microscopy (SEM). Data were subjected to the Wald test in a generalized linear model with multiple comparisons and Bonferroni adjustment, as well as two-way ANOVA (α=5%). The roughness of the conventional base resin (0.01±0.04) was lower than that of the conventional tooth (0.14±0.04) (p=0.023) and 3D-printed base (0.18±0.08) (p<0.001). For wettability, conventional resin (84.20±5.57) showed a higher contact angle than the 3D-printed resin (60.58±6.18) (p<0.001). Higher microbial loads of S. mutans (p=0.023) and S. aureus (p=0.010) were observed on the surface of the conventional resin (S. mutans: 5.48±1.55; S. aureus: 7.01±0.57) compared to the 3D-printed resin (S. mutans: 4.11±1.96; S. aureus: 6.42±0.78). The adhesion of C. albicans was not affected by surface characteristics. The conventional base resin showed less roughness than the conventional dental resin and the printed base resin. The 3D-printed resins for base and tooth showed less hydrophobicity and less adhesion of S. mutans and S. aureus than conventional resins.

Formation of the complete technological bases of machine parts for mechanical processing

The paper examines the problems of developing theoretical conditions and obtaining practical results for the formation of technological bases for parts during their machining. In this case, the basis is the information model of the geometric image of the part, which contains information about the nature of the surfaces of the parts and their mutual reference in the considered coordinate system, as well as the set of required surfaces for the orientation of each surface separately. Taking into account the quantitative and qualitative characteristics of surfaces with different structural and technological content, the technological limits of their use in the basing of parts are determined. The conditions were determined and the requirements for technological bases were formulated. From the set of technological parts, installation bases were identified and arranged, taking into account ensuring the required level of their processing with the least possible transitions. At the same time, the order of installation bases of parts is carried out on their abstract model, reflecting their structure. On the basis of the established assembly bases of parts, taking into account the requirements for the orientation of their surfaces in relation to the considered coordinate system, as well as the technological capabilities of each surface, sets of bases for the corresponding technological process are formed and their sequence of application is determined on the basis of the accepted structure of the general machining of parts. The results of the formation of a set of technological bases are presented on the example of a pulley hub for engine crankshafts for their subsequent mechanical processing.

Composite ab initio vibrational spectroscopy and thermochemistry of low-valency lanthanide compounds: europium dihalides EuX2 (X = F, Cl, Br, I).

A unique diversity in chemical properties of lanthanide compounds making them very useful in various important applications stems not least from the existence of less common Ln oxidation states, in particular +2. However, the molecular properties of low-valency lanthanide compounds are not yet well studied even for the most stable divalent Ln-containing species, such as europium dihalides. In this paper, highly accurate molecular structures, vibrational spectra, and atomisation energies of the europium dihalides EuX2 (X = F, Cl, Br, I) are obtained at the complete basis set CCSD(T) level. All of the EuX2 species are calculated to be non-linear (C2v) exhibiting a regular increase in X-Eu-X bond angle on passing through the halogen series (F → Cl → Br → I), from 117° in EuF2 to 141° in EuI2, which is accompanied by a rapid decrease in the barriers to linearity, h = E(D∞h) - E(C2v), from 2180 cm-1 to 166 cm-1, respectively. The Eu-X bonds in EuX2 appear to be longer but energetically stronger than those in the respective monohalides EuX, whose properties are studied in this work at the same level of theory as EuX2. The performance of the Ln 4f-in-core pseudopotential (PP) approximation for EuX2 is assessed by comparing the Eu PP-based coupled-cluster (CC) calculations with all-electron CC benchmarks. Incorporating the Eu 4f electrons into the PP is shown to cause large errors: up to 10 deg. in X-Eu-X bond angles, 80% in barriers to linearity, and 0.05 Å in the Eu-X bond lengths, which proves the necessity of an explicit treatment of 4f electrons if high accuracy is the goal. The present results set a benchmark in the field of low-valency lanthanide chemistry, in particular for the calibration of DFT functionals.

Theoretical and kinetic study of the thermal decomposition mechanism of long chain aldehydes

The mechanism of decomposition of the butanal and pentanal long chain aldehydes was investigated using the ab initio transition state theory-based master equation approach. The rate constants of the homolytic bond scission reactions of butanal and pentanol leading to the formation of CHO+C3H7, CH2CHO+C2H5, C2H4CHO+CH3, C3H7CO+H, C2H5ĊHCHO+H and CH2CHO+C3H7, C2H4CHO+C2H5, C3H6CHO+CH3, C4H9CO+H, C3H7ĊHCHO+H, respectively, as well as of the reverse barrierless recombination channels, were determined using Variable Reaction Coordinate Transition State Theory. The potential energy surfaces were determined at the multireference CASPT2/aug-cc-pVTZ level on ωB97X-D/jun-cc-pVTZ structures, while stochastic samplings were performed at the CASPT2 level using a (4e,4o) active space. Rate laws for the alkyl+R-CHO, H+R-ĊHCHO, and H+R-ĊO classes of reactions were then determined. Rate constants of H-abstraction reactions and of the three body butanal →CO+H2+C3H6 channel were determined using ωB97X-D/jun-cc-pVTZ structures and Hessians and CCSD(T) energies, extrapolated to the complete basis set. It was found that the calculated homolytic bond scission reactions are faster by a factor of 2–3 with respect to literature previous estimates. The calculated reaction rates were inserted in the CRECK kinetic scheme and used to simulate literature speciation data of butanal and pentanal pyrolysis in shock tubes and ignition delay times, finding that their inclusion into the kinetic scheme enhances the predictive capabilities of the mechanism. The aldehyde decomposition mechanism and the rate constants determined in this study are suitable to be used to interpret and predict the reactivity of aldehydes in a wide range of temperatures and pressures.

The electronic structure of diatomic nickel oxide.

The nature of the Ni-O bond is relevant to catalytic and environmental applications. The vibrational frequency and electronic structure of NiO were calculated using CASSCF, icMRCI+Q, CCSD(T), and DFT. CASSCF predicted a quintet state (5Σ-) ground state for the equilibrium bond distance with a state crossing at 1.65 Å, where the triplet (3Σ-) state becomes of lower energy. These states arise from the 3d8(3F)4s2 (3F) and 3d9(2D)4s1 (3D) configurations of Ni. The icMRCI+Q method predicts a triplet (3Σ-) ground state and does not predict a state crossing with the quintet. This state has significant ionic character with the 2pz of O bonding with the 4s/3dz2 of the Ni to form a σ bond. The NiO frequency at the icMRCI+Q level of 835.0 cm-1 is in excellent agreement with experiment; the value of re is 1.5992 Å at this computational level. CCSD(T) predicts ωe = 888.80 cm-1 when extrapolated to the complete basis set limit. Frequencies predicted using CCSD(T) deviate from experiment consistent with the calculations showing large multireference character. A wide array of density functionals were benchmarked. Of the 43 functionals tested, the ones that gave the best prediction of the frequency are ωB97XD, CAM-B3LYP, and τ-HCTH with respective values of 831.8, 838.3, and 837.4 cm-1 respectively. The bond dissociation energy (BDE) of NiO is predicted to be 352.4 kJ mol-1 at the Feller-Peterson-Dixon (FPD) level in good agreement with one of the experimental values. The calculated BDEs at the DFT level are sensitive to the choice of functional and atomic asymptote. Sixteen functionals predicted the BDE within 20 kJ mol-1 of the FPD value.

Generalized Energy-Based Fragmentation DLPNO-CCSD(T) Approach at Complete Basis Set Limit and Its Application to Benzene Clusters

Generalized Energy-Based Fragmentation DLPNO-CCSD(T) Approach at Complete Basis Set Limit and Its Application to Benzene Clusters

Quantitative kinetics of the atmospheric reaction between isocyanic acid and hydroxyl radicals: post-CCSD(T) contribution, anharmonicity, recrossing effects, torsional anharmonicity, and tunneling.

Hydroxyl radicals (OH) are the most important atmospheric oxidant, initiating atmospheric reactions for the chemical transformation of volatile organic compounds. Here, we choose the HNCO + OH reaction as a prototype reaction because it contains the fundamental reaction processes for OH radicals: H-abstraction reaction by OH and OH addition reaction. However, its kinetics are unknown under atmospheric conditions. We investigate the reaction of HNCO with OH by using the GMM(P).L method close to the accuracy of single, double, triple, and quadruple excitations and noniterative quintuple excitations with a complete basis set (CCSDTQ(P)/CBS) as benchmark results and a dual-level strategy for kinetics calculations. The calculated rate constant of HNCO + OH is in good agreement with the experimental data available at the temperatures between 620 and 2500 K. We find that the rate constant cannot be correctly obtained by using experimental data to extrapolate the atmospheric temperature ranges. We find that the post-CCSD(T) contribution is very large for the barrier height with the value of -0.85 kcal mol-1 for the H-abstraction reaction, while the previous investigations were done up to the CCSD(T) level. Moreover, we also find that recrossing effects, tunneling, torsional anharmonicity, and anharmonicity are important for obtaining quantitative kinetics in the OH + HNCO reaction.

Fulminic acid: a quasibent spectacle.

Fulminic acid (HCNO) played a critical role in the early development of organic chemistry, and chemists have sought to discern the structure and characteristics of this molecule and its isomers for over 200 years. The mercurial nature of the extremely flat H-C-N bending potential of fulminic acid, with a nearly vanishing harmonic vibrational frequency at linearity, remains enigmatic and refractory to electronic structure theory, as dramatic variation with both orbital basis set and electron correlation method is witnessed. To solve this problem using rigorous electronic wavefunction methods, we have employed focal point analyses (FPA) to ascertain the ab initio limit of optimized linear and bent geometries, corresponding vibrational frequencies, and the HCN + O(3P) → HCNO reaction energy. Electron correlation treatments as extensive as CCSDT(Q), CCSDTQ(P), and even CCSDTQP(H) were employed, and complete basis set (CBS) extrapolations were performed using the cc-pCVXZ (X = 4-6) basis sets. Core electron correlation, scalar relativistic effects (MVD1), and diagonal Born-Oppenheimer corrections (DBOC) were all included and found to contribute significantly in determining whether vibrationless HCNO is linear or bent. At the all-electron (AE) CCSD(T)/CBS level, HCNO is a linear molecule with ω5(H-C-N bend) = 120 cm-1. However, composite AE-CCSDT(Q)/CBS computations give an imaginary frequency (51i cm-1) at the linear optimized geometry, leading to an equilibrium structure with an H-C-N angle of 173.9°. Finally, at the AE-CCSDTQ(P)/CBS level, HCNO is once again linear with ω5 = 45 cm-1, and inclusion of both MVD1 and DBOC effects yields ω5 = 32 cm-1. A host of other topics has also been investigated for fulminic acid, including the dependence of re and ωi predictions on a variety of CBS extrapolation formulas, the question of multireference character, the N-O bond energy and enthalpy of formation, and issues that give rise to the quasibent appellation.

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part II: linear pentanol isomers.

High-level ab initio calculations are conducted for studying the kinetics of three linear pentanol radicals generated through H-atom abstraction reactions. The species involved are optimized using the M06-2X/6-311++G(d,p) level of theory, while a relaxed scan at the M06-2X/6-31g level of theory with 10° increments is used for the hindrance potential for low-frequency torsional modes. Single-point energies for all stationary points are obtained through the QCISD(T) and MP2 methods in combination with cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets, which can be extrapolated to the complete basis set (CBS) limit. The rate constants and branching ratios for isomerization and decomposition reactions are computed over a temperature range of 250-2000 K and a pressure range of 0.01-100 atm. Isomerization reactions are dominant at low temperatures, while decomposition reactions are more dominant at high temperatures. The branching ratio of the isomerization reaction exhibits a slight decrease with increasing pressure, while the trend for decomposition reactions depends on the type of the breaking bond. Based on the calculations for five branched pentanol radicals in part I, kinetics of linear and branched pentanol radicals are compared in this work and the results reveal that, for the same kind of β-scission reaction at similar positions of linear and branched pentanol radicals, the rate constants of branched ones are faster than those of linear ones at low temperatures. The hydroxyl group adjacent to the breaking bond can increase the β-scission reaction rate constants, while the effect can be ignored when the hydroxyl group is not adjacent to the breaking bond. Moreover, compared to when the hydroxyl group is located in the middle of the carbon chain, its positioning at the chain's end yields a more noticeable impact on the products and rate constants of C-O bond and O-H bond β-scission reactions. Besides, when incorporating calculated rate constants into the CRECK model, the updated mechanism shows a better performance for ignition delay times of 1-pentanol in the NTC range but exhibits lower reactivity at higher temperatures. The simulation of speciation profiles also shows better agreement with the experimental data obtained using a flow reactor.

Towards efficient quantum computing for quantum chemistry: reducing circuit complexity with transcorrelated and adaptive ansatz techniques.

The near-term utility of quantum computers is hindered by hardware constraints in the form of noise. One path to achieving noise resilience in hybrid quantum algorithms is to decrease the required circuit depth - the number of applied gates - to solve a given problem. This work demonstrates how to reduce circuit depth by combining the transcorrelated (TC) approach with adaptive quantum ansätze and their implementations in the context of variational quantum imaginary time evolution (AVQITE). The combined TC-AVQITE method is used to calculate ground state energies across the potential energy surfaces of H4, LiH, and H2O. In particular, H4 is a notoriously difficult case where unitary coupled cluster theory, including singles and doubles excitations, fails to provide accurate results. Adding TC yields energies close to the complete basis set (CBS) limit while reducing the number of necessary operators - and thus circuit depth - in the adaptive ansätze. The reduced circuit depth furthermore makes our algorithm more noise-resilient and accelerates convergence. Our study demonstrates that combining the TC method with adaptive ansätze yields compact, noise-resilient, and easy-to-optimize quantum circuits that yield accurate quantum chemistry results close to the CBS limit.

Моніторинг циркулярності економічних систем

In the conditions of the transformation of modern society, due to the spread and introduction of the Internet, digital data, robotics, and artificial intelligence, all spheres of human life are changing. Over the past decade, the circular economy has been actively implemented in developed countries, eliminating the outdated linear economy, the disadvantages of which are the depletion of natural resources and the aggravation of environmental problems. The construction of a circular economy involves global changes at all stages of the production process, starting from the production and sales chain to the introduction of new business models, preservation, and extension of the service life of products (conservation of natural resources), recycling of waste into a resource, as well as the introduction of new forms of conscious consumer behavior. A critical condition for activating the intensification of the transition to the circular economy model is creating a comprehensive methodological tool for assessing its development, which is necessary for effective strategic and program planning at the state level. It is noted that low rates characterize the progress of circular transformations. Along with this, the methodical level of assessing the circularity of economic systems of different levels and their effectiveness remains quite complex and debatable. Many international organizations, national governments, and their associations are searching for effective methods and approaches to evaluating the development of circular processes. The main methodical approaches that are widespread in practice today are analyzed: the umbrella approach, material flow approach, circulation, assessment based on standards, and integrated approach. Two critical directions of evaluating the circularity of economic processes (technical and biological) are currently popular, characterized by their monitoring and evaluation indicators system. The multifaceted nature of indicators for evaluating circular macro-level processes and the variety of conditions in which these processes are carried out led to the understanding of the need to create appropriate circular economy standards that would form a complete methodological basis for monitoring, comparison, and evaluation. Keywords: monitoring, economy, system, indicators, sustainable development.