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The x-ray restrained wave function (XRW) method is a quantum crystallographic technique to extract wave functions compatible with experimental x-ray diffraction data. The approach looks for wave functions that minimize the energies of the investigated systems and also reproduce sets of x-ray structure factors. Given the strict relationship between x-ray structure factors and electron distributions, the strategy practically allows determining wave functions that correspond to given (usually experimental) electron densities. In this work, the capabilities of the XRW approach were further tested. The aim was to evaluate whether the XRW technique could serve as a tool for suggesting new exchange-correlation functionals for density functional theory or refining existing ones. Additionally, the ability of the method to address the influences of the crystalline environment was also assessed. The outcomes of XRW computations were thus compared to those of traditional gas-phase, embedding quantum mechanics/molecular mechanics, and fully periodic calculations. The results revealed that, irrespective of the initial conditions, the XRW computations practically yield a consensus electron density, in contrast to the currently employed density functional approximations (DFAs), which tend to give a too large range of electron distributions. This is encouraging in view of exploiting the XRW technique to develop improved functionals. Conversely, the calculations also emphasized that the XRW method is limited in its ability to effectively address the influences of the crystalline environment. This underscores the need for a periodic XRW technique, which would allow further untangling the shortcomings of DFAs from those inherent to the XRW approach. [ABSTRACT FROM AUTHOR]

Acetaldehyde is a very relevant atmospheric species whose photodissociation has been extensively studied in the first absorption band both experimentally and theoretically. Very few works have been reported on acetaldehyde photodissociation at higher excitation energies. In this work, the photodissociation dynamics of acetaldehyde is investigated by means of high-level multireference configuration interaction ab initio calculations. Five different fragmentation pathways of acetaldehyde are explored by calculating the potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distances. The excitation energy range covered in the study is up to 10 eV, nearly the ionization energy of acetaldehyde. We intend to rationalize the available experimental results and, in particular, to elucidate why some of the studied fragmentation pathways are experimentally observed in the different excitation energy regions and some others are not. Based on the shape of the calculated potential curves, we are able to explain the main findings of the available experiments, also suggesting possible dynamical dissociation mechanisms in the different energy regions. Thus, the reported potential curves are envisioned as a useful tool to interpret the currently available experiments as well as future ones on acetaldehyde photodissociation at excitation wavelengths in the range studied here. [ABSTRACT FROM AUTHOR]

Quantum Dot Cellular Automata (QCA) is an emerging trend in the field of nanoelectronics, and computing can be regarded as an alternative to the traditional complementary metal–oxide–semiconductor technology. The paper is devoted to the study of the key functional properties of the cells for molecular QCA based on mixed valence molecules. The theoretical results for the heat dissipation under the conditions of the fast nonadiabatic switching event and cell–cell response function are obtained in the framework of the quantum-mechanical vibronic approach. These results are parameterized using the previous reliable ab initio calculations performed for oxidized norbornadiene and its polycyclic derivatives with variable lengths of the bridge. The comparative analysis of the dimeric and bidimeric molecular cells composed of these compounds is given. It is underlined that the conditions of a strong non-linear response and a low heat release are contradictory. However, despite this problem, a parametric regime is proposed, which provides a low heat release in combination with a strong nonlinear response of the working cell to the electric field induced by the polarized driver cell. [ABSTRACT FROM AUTHOR]

In this work, the Common Model of Multi-phase Strength and Equation of State (CMMP) model was applied to tin. Specifically, calibrations of the strength-specific elements of the CMMP foundation were developed with a combination of experiments and theory, and then the model was validated experimentally. The first element of the foundation is a multi-phase analytic treatment of the melt temperature and the shear modulus for the solid phases. These models were parameterized for each phase based on ab initio calculations using the software VASP (Vienna Ab initio Simulations Package) based on density functional theory. The shear modulus model for the ambient β phase was validated with ultrasonic sound speed measurements as a function of pressure and temperature. The second element of the foundation is a viscoplastic strength model for the β phase, upon which strength for inaccessible higher-pressure phases can be scaled as necessary. The stress–strain response of tin was measured at strain rates of 10 − 3 to 3 × 10 3 s − 1 and temperatures ranging from 87 to 373 K. The Preston–Tonks–Wallace (PTW) strength model was fit to that data using Bayesian model calibration. For validation, six forward and two reverse Taylor impact experiments were performed at different velocities to measure large plastic deformation of tin at strain rates up to 10 5 s − 1 . The PTW model accurately predicted the deformed shapes of the cylinders, with modest discrepancies attributed to the inability of PTW to capture the effects of twinning and dynamic recrystallization. Some material in the simulations of higher velocity Taylor cylinders reached the melting temperature, thus testing the multiphase model because of the presence of a second phase, the liquid. In simulations using a traditional modeling approach, the abrupt reduction of strength upon melt resulted in poor predictions of the deformed shape and non-physical temperatures. With CMMP, the most deformed material points evolved gradually to a mixed solid–liquid but never a fully liquid state, never fully lost strength, stayed at the melt temperature as the latent heat of fusion was absorbed, and predicted the deformed shape well. [ABSTRACT FROM AUTHOR]

Ethane ( C 2 H 6 ) is anticipated to be the most stable compound within the carbon–hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C 2 H 6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2–5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding. [ABSTRACT FROM AUTHOR]

The isotope shifts in electron affinities of Pb were measured by Walter et al. [Phys. Rev. A 106, L010801 (2022)] to be −0.002(4) meV for 207–208Pb and −0.003(4) meV for 206–208Pb by scanning the threshold of the photodetachment channel Pb− ( S 3 / 2 ◦ 4 ) − Pb (3P0), while Chen and Ning reported 0.015(25) and −0.050(22) meV for the isotope shifts on the binding energies measured relative to 3P2 using the SEVI method [J. Chem. Phys. 145, 084303 (2016)]. Here we revisited these isotope shifts by using our second-generation SEVI spectrometer and obtained −0.001(15) meV for 207–208Pb and −0.001(14) meV for 206–208Pb, respectively. In order to aid the experiment by theory, we performed the first ab initio theoretical calculations of isotope shifts in electron affinities and binding energies of Pb, as well as the hyperfine structure of 207Pb−, by using the MCDHF and RCI methods. The isotope shifts in electron affinities of 207–208Pb and 206–208Pb are −0.0023(8) and −0.0037(13) meV for the 3P0 channel, respectively, in good agreement with Walter et al.'s measurements. The isotope shifts in binding energies relative to 3P1,2, −0.0015(8) and −0.0026(13) meV for 207–208Pb and 206–208Pb, respectively, are compatible with the present measurements. The hyperfine constant for the ground state of 207Pb− obtained by the present calculations, A ( S 3 / 2 ◦ 4 ) = − 1118 MHz, differs by a factor of 3 from the previous estimation by Bresteau et al. [J. Phys. B: At., Mol. Opt. Phys. 52, 065001 (2019)]. The reliability is supported by the good agreement between the theoretical and experimental hyperfine parameters of 209Bi. [ABSTRACT FROM AUTHOR]

This study was focused on the photochemistry of OAlOH and three possible pathways, which were studied with high-level multireference configuration interaction ab initio calculations. We computed cuts of the six-dimensional potential energy surfaces for the ground, the lowest singlet and triplet excited states, and probed the photodissociation mechanisms and the stabilities. The OAlOH electronic spectrum, with an energy reaching 7.15 eV, contained four prominent peaks. Photodissociation to AlO, OH, and AlOH constituted a plausible mechanism within the deep-UV range (λ = 250.4 nm). Our data indicated the photostability of OAlOH in the near-UV‒Vis region, so detection with laser-induced fluorescence is possible. Fluorescence and phosphorescence may occur upon excitation at 363.5 nm. The roles of OAlOH in the photochemical reactions of Al-bearing molecules in the upper atmosphere and VY Canis Majoris are discussed. [ABSTRACT FROM AUTHOR]

The in-plane thermal conductivity of hexagonal boron nitride (h-BN) with varying thicknesses is a key property that affects the performance of various applications from electronics to optoelectronics. However, the transition of the thermal conductivity from two-dimensional (2D) to three-dimensional (3D) h-BN remains elusive. To answer this question, we have developed a machine learning interatomic potential within the neuroevolution potential (NEP) framework for h-BN, achieving a high accuracy akin to ab initio calculations in predicting its thermal conductivity and phonon transport from monolayer to multilayers and bulk. Utilizing molecular dynamics simulations based on the NEP, we predict the thermal conductivity of h-BN with a thickness up to ∼100 nm, demonstrating that its thermal conductivity quickly decreases from the monolayer and saturates to the bulk value above four layers. The saturation of its thermal conductivity is attributed to the little change in phonon group velocity and lifetime as the thickness increases beyond four layers. In particular, the weak thickness dependence of phonon lifetime in h-BN with a nanoscale thickness results from its extremely high phonon focusing along the in-plane direction. This research bridges the knowledge gap of phonon transport between 2D and 3D h-BN and will benefit the thermal design and performance optimization of relevant applications. [ABSTRACT FROM AUTHOR]

Face-to-face annealed and sputter-deposited aluminum nitride (FFA Sp-AlN) has potential in deep-ultraviolet light-emitting devices. Herein, the effects of the substrate off-cut angle (θsub) from an r-plane sapphire toward the c-axis projection direction and sputtering temperature (Tsp) on the crystallinity and surface morphology of a-plane AlN films are investigated. Increasing θsub in the minus-off direction, which occurs when the substrate surface approaches the sapphire c-plane, and lowering Tsp suppress the mixing of anomalous non-a-direction oriented domains. This reduced mixing enhances the surface flatness and crystallinity of a-plane FFA Sp-AlN. Moreover, the c-axis direction of the a-plane AlN film is inverted depending on the substrate off-cut angle. Ab initio calculations indicate that the interface stability between the r-plane sapphire substrate and the a-plane AlN film can explain the dependence of the crystallinity and c-axis orientation of FFA Sp-AlN on the surface off-cut of the r-plane sapphire. [ABSTRACT FROM AUTHOR]

Phosphate-based glasses (PBGs) in the CaO–Na2O–P2O5 system have diverse applications as biomaterials due to their unique dissolution properties. A reactive force field (ReaxFF) has been developed to simulate these materials at the atomic level. The ReaxFF parameters of PBGs, including the interaction between phosphorus and calcium atoms, have been developed using a published code based on genetic algorithms. The training data, including the atomic charges, atomic forces, bond and angle parameters, and different differential energies, are chosen and measured from static quantum-mechanical calculations and ab initio molecular dynamics of PBGs. We did different short- and medium-range structural analyses on the bulk simulated PBGs with different compositions to validate the developed potential. Radial and angular distribution functions and coordination numbers of network formers and modifiers, as well as the network connectivity of the glass, are in agreement with experimental and previous simulations using both shell-model classical force fields and ab initio simulated data; for example, the coordination number of phosphorus is 4.0. This successful development of ReaxFF parameters being able to describe the bulk PBGs enables us to work on the dissolution behavior of the glasses, including the interaction of water molecules with PBGs, in future works. [ABSTRACT FROM AUTHOR]

C H 3 + , a cornerstone intermediate in interstellar chemistry, has recently been detected for the first time by using the James Webb Space Telescope. The photodissociation of this ion is studied here. Accurate explicitly correlated multi-reference configuration interaction ab initio calculations are done, and full-dimensional potential energy surfaces are developed for the three lower electronic states, with a fundamental invariant neural network method. The photodissociation cross section is calculated using a full-dimensional quantum wave packet method in heliocentric Radau coordinates. The wave packet is represented in angular and radial grids, allowing us to reduce the number of points physically accessible, requiring to push up the spurious states appearing when evaluating the angular kinetic terms, through projection technique. The photodissociation spectra, when employed in astrochemical models to simulate the conditions of the Orion bar, result in a lesser destruction of C H 3 + compared to that obtained when utilizing the recommended values in the kinetic database for astrochemistry. [ABSTRACT FROM AUTHOR]

An accurate description of the long-range (LR) interaction is essential for understanding the collision between cold or ultracold molecules. However, to our best knowledge, there lacks a general approach to construct the intermolecular potential energy surface (IPES) between two arbitrary molecules and/or atoms in the LR region. In this work, we derived analytical expressions of the LR interaction energy, using the multipole expansion of the electrostatic interaction Hamiltonian and the non-degenerate perturbation theory. To make these formulae practical, we also derived the independent Cartesian components of the electrostatic properties, including the multipole moments and polarizabilities, of the monomer for a given symmetry using the properties of these components and the group-theoretical methods. Based on these newly derived formulae, we developed a FORTRAN program, namely ABLRI, which is capable of calculating the interaction energy between two arbitrary monomers both in their non-degenerate electronic ground states at large separations. To test the reliability of this newly developed program, we constructed IPESs for the electronic ground state of H2O–H2 and O2–H systems in the LR region. The interaction energy computed by our program agreed well with the ab initio calculation, which shows the validity of this program. [ABSTRACT FROM AUTHOR]

Thorium nitrides have been the topic of intense studies due to their prospective applications as advanced nuclear fuels. The phase diagram of the Th–N scheme, however, continues unknown at low temperatures and extremely high pressures. In this article, we examine the Th–N system's phase diagram up to 300 GPa from the first-principle approach using universal structure predictor: evolutionary Xtallography (USPEX) method. Apart from the experimentally observed phase (ThN, Th2N3, and Th3N4), there are several unique chemical stoichiometries, i.e., ThN3, ThN4, ThN6, ThN8, ThN10, and ThN12 are found to have stability fields on the Th–N phase diagram at pressure of 3.0, 32, 100, 42, 28, and 236 GPa along with previously predicted composition ThN2 at 3.5 GPa. The structural stability of the predicted compositions is further assessed by evaluating the elastic and dynamic stability. Out of all above mentioned compositions, ThN3 is possibly a metastable one at 0 GPa. Electronic structure calculations predict that all newly discovered compositions are metallic except ThN10, which is semi-metallic at high pressures. Further, we predict that ThN4 and ThN6 have high electron–phonon coupling constant of 1.874 and 0.894 with Tc around 21.22 and 25.02 K, respectively, at 100 GPa. [ABSTRACT FROM AUTHOR]

Identifying the oxidation structure of two-dimensional interfaces is crucial to improve surface chemistry and electronic properties. Beyond graphene with only phenyl rings, a novel carbon-nitrogen material, C3N, presents an intrinsic heterogeneous surface morphology where each phenyl ring is encircled by six nitrogen atoms, yet its atomistic oxidation structure remains unclear. Here, combining a series of density functional theory calculations and ab initio molecular dynamics simulations, we demonstrate that thermodynamically favorable oxidation loci are confined to the phenyl ring, and kinetic transformations of oxidation structures are feasible along the phenyl ring, whereas those toward nitrogen atoms are proven to be extremely difficult. These results are attributed to the lower barrier of oxygen atom migration along the phenyl ring, while the significantly high barriers toward nitrogen atoms are due to the heterogeneous potential energy surface for oxygen–C3N interaction. This work highlights the significance of surface morphology on the characteristics of oxidation structure, offering insights into tunable electronic properties via confined interfacial oxidation. [ABSTRACT FROM AUTHOR]

C-incorporated amorphous silica (a-SiOC) is expected to be a significant dielectric film for miniaturized semiconductor devices. However, information on the relationship among its composition, atomic structures, and material properties remains insufficient. This study investigated the dependence of the elastic modulus on the C content in a-SiOC, employing a universal neural network interatomic potential to realize a high-accuracy and high-speed simulation of multicomponent systems. The relationship between elastic modulus and atomic network structures was explored by fabricating 480 amorphous structures through the melt-quenching method without predetermined structure assumptions. The bulk modulus increased from 45 to 60 GPa by incorporating 10% C atoms under O-poor conditions and 20% C atoms under O-rich conditions, respectively. This result is attributed to the formation of denser crosslinking atomic network structures. In particular, the C atoms bonded with the Si atoms with higher coordination under O-poor conditions, whereas they tend to bond with O atoms under O-rich conditions, breaking the SiO2 network. Large C clusters precipitated as the C fraction was increased under O-rich conditions. Gas molecules, such as CO and CO2, were also generated. These results are consistent with reported ab initio calculation results of the formation energies of C defects and gas molecules in SiO2. The findings suggest that realizing O-poor conditions during deposition is crucial for fabricating stronger dielectric films. Therefore, this work contributes to understanding the fabrication of stronger dielectric films and elucidating the underlying mechanism of C cluster formation. [ABSTRACT FROM AUTHOR]

Gallenene is a novel metallic 2D material that can provide a semiconducting counterpart if patterned into quasi-one-dimensional (quasi-1D) nanostructures, i.e., gallenene nanoribbons (GaNRs). We investigate semiconducting GaNRs as a potential channel material for future ultrascaled field-effect transistors (FETs) by employing quantum transport simulations based on Green's functions and tight-binding Hamiltonians with the orbital resolution calibrated on ab initio calculations. The impact of GaNR width downscaling from ∼6 nm down to ∼0.2 nm on the electronic, transport, and ballistic device properties is investigated for the FET channel length of 15 nm. We report current enhancement and injection velocity overshoot effects for sub-1.2 nm-wide nFETs and pFETs, with a maximum current increase of 53% in the 1.2 nm-wide GaNR pFET in comparison to the widest device. In addition, promising current-driving capabilities of n- and p-channel GaNR FETs are observed with top ballistic currents of more than 2.2 mA/μm and injection velocities of up to 2.4 × 107 cm/s. The reported data are explained by analyzing the evolution of band structure and related parameters such as injection velocity, quantum capacitance, effective transport mass etc., with increasing quantum confinement effects in ultranarrow GaNRs. Generally, we find that quasi-1D gallenene is a promising channel material for future nanoscale FETs, especially for transistor architectures based on stacked nanosheets. [ABSTRACT FROM AUTHOR]

The Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach is a method to generate fully coupled diabatic potential energy surfaces (PESs) including relativistic effects, especially spin–orbit coupling. The spin–orbit coupling of a full molecule is determined only by the atomic states of selected relativistically treated atoms. The full molecular coupling effect is obtained by a diabatization with respect to asymptotic states, resulting in the correct geometry dependence of the spin–orbit effect. The ERCAR approach has been developed over the last decade and initially only for molecules with a single relativistic atom. This work presents its extension to molecules with more than a single relativistic atom using the iodine molecule as a proof-of-principle example. The theory for the general multiple atomic ERCAR approach is given. In this case, the diabatic basis is defined at the asymptote where all relativistic atoms are separated from the remaining molecular fragment. The effective spin–orbit operator is then a sum of spin–orbit operators acting on isolated relativistic atoms. PESs for the iodine molecule are developed within the new approach and it is shown that the resulting fine structure states are in good agreement with spin–orbit ab initio calculations. [ABSTRACT FROM AUTHOR]

In this work, we propose a linear machine learning force matching approach that can directly extract pair atomic interactions from ab initio calculations in amorphous structures. The local feature representation is specifically chosen to make the linear weights a force field as a force/potential function of the atom pair distance. Consequently, this set of functions is the closest representation of the ab initio forces, given the two-body approximation and finite scanning in the configurational space. We validate this approach in amorphous silica. Potentials in the new force field (consisting of tabulated Si–Si, Si–O, and O–O potentials) are significantly different than existing potentials that are commonly used for silica, even though all of them produce the tetrahedral network structure and roughly similar glass properties. This suggests that the commonly used classical force fields do not offer fundamentally accurate representations of the atomic interaction in silica. The new force field furthermore produces a lower glass transition temperature (Tg ∼ 1800 K) and a positive liquid thermal expansion coefficient, suggesting the extraordinarily high Tg and negative liquid thermal expansion of simulated silica could be artifacts of previously developed classical potentials. Overall, the proposed approach provides a fundamental yet intuitive way to evaluate two-body potentials against ab initio calculations, thereby offering an efficient way to guide the development of classical force fields. [ABSTRACT FROM AUTHOR]

We present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA)n–H]− (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM−) H2N●SO3− at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM−●SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM− binding to a zwitterionic SA (SM−●SAz) and a canonical SA (SM−●SAc), respectively. Two N–H⋯O HBs and one superior O–H⋯O HB are formed in the lowest-lying SM−●SAc, while SM−●SAz has three moderate N–H⋯O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM−●SAc over SM−●SAz arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth. [ABSTRACT FROM AUTHOR]

Semi-experimental structures ( r e SE ) are derived from experimental ground state rotational constants combined with theoretical vibrational corrections. They permit a meaningful comparison with equilibrium structures based on high-level ab initio calculations. Typically, the vibrational corrections are evaluated with second-order vibrational perturbation theory (VPT2). The amount of error introduced by this approximation is generally thought to be small; however, it has not been thoroughly quantified. Herein, we assess the accuracy of theoretical vibrational corrections by extending the treatment to fourth order (VPT4) for a series of small linear molecules. Typical corrections to bond distances are on the order of 10−5 Å. Larger corrections, nearly 0.0002 Å, are obtained to the bond lengths of NCCN and CNCN. A borderline case is CCCO, which will likely require variational computations for a satisfactory answer. Treatment of vibrational effects beyond VPT2 will thus be important when one wishes to know bond distances confidently to four decimal places (10−4 Å). Certain molecules with shallow bending potentials, e.g., HOC+, are not amenable to a VPT2 description and are not improved by VPT4. [ABSTRACT FROM AUTHOR]

Utilization of metal tungsten (W) as the structural material or pressure scale requires accurate knowledge of the equation of state (EOS), which is far beyond the available experimental measurements. In the present work, a direct integral approach (DIA) with ultrahigh efficiency was applied to calculate the EOS of W up to 500 GPa and 3000 K with ab initio calculations. Compared with previous static compression experiments up to 150 GPa under room temperature and 35 GPa at high temperatures up to 1673 K, all the deviations of the calculated pressure are within or comparable to the uncertainty of experiments. Predictions for higher-temperature and simultaneously higher-pressure EOS up to 300 GPa and 3000 K differ slightly from the comprehensive analysis by Litasov et al. [J. Appl. Phys. 113, 133505 (2013)] via fitting available experimental data with the empirical equation. These results indicate that the EOS of crystal W obtained from DIA should be convincible, and DIA without any empirical or artificial parameters may find its wide applications for predicting thermodynamic properties of condensed matter in the future. [ABSTRACT FROM AUTHOR]

New six-dimensional ab initio potential energy surfaces (PESs) for the N2–CO2 complex, which involve the stretching vibration of N2 and the Q3 normal mode for the ν3 asymmetric stretching vibration of CO2, were constructed using the CCSD(T)-F12/AVTZ method with midpoint bond functions. Two vibrational averaged 4D interaction potentials were obtained by integrating over the two intramolecular coordinates. It was found that both PESs possess two equivalent T-shaped global minima as well as two in-plane and one out-of-plane saddle points. Based on these PESs, rovibrational bound states and energy levels were calculated applying the radial discrete variable representation/angular finite basis representation method and the Lanczos algorithm. The splitting of the energy levels between oN2–CO2 and pN2–CO2 for the intermolecular vibrational ground state is determined to be only 0.000 09 cm−1 due to the higher barriers. The obtained band origin shift is about +0.471 74 cm−1 in the N2–CO2 infrared spectra with CO2 at the ν3 zone, which coincides with the experimental data of +0.483 74 cm−1. The frequencies of the in-plane geared-bending for N2–CO2 at the ν3 = 0 and 1 states of CO2 turn out to be 21.6152 and 21.4522 cm−1, the latter reproduces the available experimental 21.3793 cm−1 value with CO2 at the ν3 zone. The spectral parameters fitted from the rovibrational energy levels show that this dimer is a near prolate asymmetric rotor. The computed microwave transitions as well as the infrared fundamental and combination bands for the complex agree well with the observed data. [ABSTRACT FROM AUTHOR]

A new non-empirical ab initio intermolecular force field (NICE-FF in buffered 14-7 potential form) has been developed for nucleic acids and beyond based on the dimer interaction energies (IEs) calculated at the spin component scaled-MI-second order Møller–Plesset perturbation theory. A fully automatic framework has been implemented for this purpose, capable of generating well-polished computational grids, performing the necessary ab initio calculations, conducting machine learning (ML) assisted force field (FF) parametrization, and extending existing FF parameters by incorporating new atom types. For the ML-assisted parametrization of NICE-FF, interaction energies of ∼18 000 dimer geometries (with IE < 0) were used, and the best fit gave a mean square deviation of about 0.46 kcal/mol. During this parametrization, atom types apparent in four deoxyribonucleic acid (DNA) bases have been first trained using the generated DNA base datasets. Both uracil and hypoxanthine, which contain the same atom types found in DNA bases, have been considered as test molecules. Three new atom types have been added to the DNA atom types by using IE datasets of both pyrazinamide and 9-methylhypoxanthine. Finally, the last test molecule, theophylline, has been selected, which contains already-fitted atom-type parameters. The performance of NICE-FF has been investigated on the S22 dataset, and it has been found that NICE-FF outperforms the well-known FFs by generating the most consistent IEs with the high-level ab initio ones. Moreover, NICE-FF has been integrated into our in-house developed crystal structure prediction (CSP) tool [called FFCASP (Fast and Flexible CrystAl Structure Predictor)], aiming to find the experimental crystal structures of all considered molecules. CSPs, which were performed up to 4 formula units (Z), resulted in NICE-FF being able to locate almost all the known experimental crystal structures with sufficiently low RMSD20 values to provide good starting points for density functional theory optimizations. [ABSTRACT FROM AUTHOR]

TurboGenius is an open-source Python package designed to fully control ab initio quantum Monte Carlo (QMC) jobs using a Python script, which allows one to perform high-throughput calculations combined with TurboRVB [Nakano et al. J. Phys. Chem. 152, 204121 (2020)]. This paper provides an overview of the TurboGenius package and showcases several results obtained in a high-throughput mode. For the purpose of performing high-throughput calculations with TurboGenius, we implemented another open-source Python package, TurboWorkflows, that enables one to construct simple workflows using TurboGenius. We demonstrate its effectiveness by performing (1) validations of density functional theory (DFT) and QMC drivers as implemented in the TurboRVB package and (2) benchmarks of Diffusion Monte Carlo (DMC) calculations for several datasets. For (1), we checked inter-package consistencies between TurboRVB and other established quantum chemistry packages. By doing so, we confirmed that DFT energies obtained by PySCF are consistent with those obtained by TurboRVB within the local density approximation (LDA) and that Hartree–Fock (HF) energies obtained by PySCF and Quantum Package are consistent with variational Monte Carlo energies obtained by TurboRVB with the HF wavefunctions. These validation tests constitute a further reliability check of the TurboRVB package. For (2), we benchmarked the atomization energies of the Gaussian-2 set, the binding energies of the S22, A24, and SCAI sets, and the equilibrium lattice parameters of 12 cubic crystals using DMC calculations. We found that, for all compounds analyzed here, the DMC calculations with the LDA nodal surface give satisfactory results, i.e., consistent either with high-level computational or with experimental reference values. [ABSTRACT FROM AUTHOR]

The optical spectra of the palladium monosulfide (PdS) molecule in gas phase have been investigated for the first time through laser-induced fluorescence (LIF) and single-vibronic-level (SVL) emission spectroscopies. The I3Σ− − X3Σ− transition system containing 16 vibronic bands was identified in the LIF spectra, covering the energy range of 22 030–23 400 cm−1. The spectra with rotational resolution allowed for the determination of the molecular constants in both the ground X and excited I electronic states, involving the spin–orbit splitting, rotational constant, vibrational frequency, and isotope shift. Isotopically resolved SVL emission spectra permitted the observation of the spin–orbit splitting, vibrational frequency, and vibrational isotope shift of the X3Σ−0+,1 and A3Π2,1,0−,0+ states as they transitioned from the excited I state to the vibrational levels of the X and A states. Ab initio calculations presented plenty of the Λ-S and Ω states of PdS below 28 000 cm−1 and provided strong support for the assignments of the experimental observation. [ABSTRACT FROM AUTHOR]

The choice of exchange functional is a critical factor in determining the energy bandgap of semiconductors. Ab initio calculations using different exchange functionals, including the conventional generalized-gradient approximation (GGA) functionals, meta-GGA functionals, and hybrid functionals, show significant differences in the calculated energy bandgap for semiconducting half-Heusler compounds. These compounds, which have 18 valence electrons per unit cell, are of great interest due to their thermoelectric properties, making them suitable for energy conversion applications. In addition, accounting for electronic correlations using the G W method also affects the calculated energy bandgaps compared to standard GGA calculations. The variations in calculated energy bandgaps are specific to each material when using different functionals. Hence, a detailed investigation of the electronic properties of each compound is necessary to determine the most appropriate functional for an accurate description of the electronic properties. Our results indicate that no general rules can be established and a comparison with experimental results is required to determine the most appropriate functional. [ABSTRACT FROM AUTHOR]

The quantum chemistry community has developed analytic forces for approximate electronic excited states to enable walking on excited state potential energy surfaces (PES). One can thereby computationally characterize excited state minima and saddle points. Always implicit in using this machinery is the fact that an excited state PES only exists within the realm of the Born-Oppenheimer approximation, where the nuclear and electronic degrees of freedom separate. This work demonstrates through ab initio calculations and simple nonadiabatic dynamics that some excited state minimum structures are fantastical: they appear to exist as stable configurations only as a consequence of the PES construct, rather than being physically observable. Each fantastical structure exhibits an unphysically high predicted harmonic frequency and associated force constant. This fact can serve as a valuable diagnostic of when an optimized excited state structure is non-observable. The origin of this phenomenon can be attributed to the coupling between different electronic states. As PESs approach one another, the upper surface can form a minimum that is very close to a near-touching point. The force constant, evaluated at this minimum, relates to the strength of the electronic coupling rather than to any characteristic excited state vibration. Nonadiabatic dynamics results using a Landau-Zener model illustrate that fantastical excited state structures have extremely short lifetimes on the order of a few femtoseconds. Their appearance in a calculation signals the presence of a nearby conical intersection through which the system will rapidly cross to a lower surface. [ABSTRACT FROM AUTHOR]

Constructing metal-semiconductor interfaces by loading metal atoms onto two-dimensional material to build atomically dispersed single-atom catalysts (SACs) has emerged as a new frontier for improving atom utilization and designing multifunctional electrocatalysts. Nowadays, studies on black phosphorus nanosheets in electrocatalysis have received much attention and the successful preparation of metal nanoparticle/black phosphorus (BP) hybrid electrocatalysts indicates BP nanosheets can serve as a potential support platform for SACs. Herein, by using large-scale ab initio calculations, we explored a large composition space of SACs with transition metal atoms supported on BP monolayer (M-BP) and built a comprehensive picture of activity trend, stability, and electronic origin towards oxygen reduction and evolution reaction (ORR and OER) and hydrogen evolution reaction (HER). The results show that the catalytic activity can be widely tuned by reasonable regulation of metal atoms. Ni-, Pd-, and Pt-BP could effectively balance the binding strength of the target intermediates, thus achieving efficient bifunctional activity for OER and ORR. Favorable bifunctional catalytic performance for OER and HER can be realized on Rh-BP. Especially, Pt-BP exhibits promising trifunctional activity towards OER, ORR, and HER. Multiple-level corrections among overpotential, Gibbs free energy, orbital population, and d-band center reveal that the trend and origin of catalytic activity are intrinsically determined by the d-band center of metal sites. The thermodynamic and dynamic stability simulations demonstrate that the active metal centers are firmly anchored on BP substrate with intact M-P bonds. These findings provide a theoretical basis for the rational design of BP-based SACs toward promising multifunctional activity. [ABSTRACT FROM AUTHOR]

Modeling environments that are not in local thermal equilibrium, such as protoplanetary disks or planetary atmospheres, with molecular spectroscopic data from space telescopes requires knowledge of the rate coefficients of rovibrationally inelastic molecular collisions. Here, we present such rate coefficients in a temperature range from 10 to 500 K for collisions of CO2 with He atoms in which CO2 is (de)excited in the bend mode. They are obtained from numerically exact coupled-channel (CC) calculations as well as from calculations with the less demanding coupled-states approximation (CSA) and the vibrational close-coupling rotational infinite-order sudden (VCC-IOS) method. All of the calculations are based on a newly calculated accurate ab initio four-dimensional CO2–He potential surface including the CO2 bend (ν2) mode. We find that the rovibrationally inelastic collision cross sections and rate coefficients from the CSA and VCC-IOS calculations agree to within 50% with the CC results at the rotational state-to-state level, except for the smaller ones and in the low energy resonance region, and to within 20% for the overall vibrational quenching rates except for temperatures below 50 K where resonances provide a substantial contribution. Our CC quenching rates agree with the most recent experimental data within the error bars. We also compared our results with data from Clary et al. calculated in the 1980s with the CSA [A. J. Banks and D. C. Clary, J. Chem. Phys. 86, 802 (1987)] and VCC-IOS [D. C. Clary, J. Chem. Phys. 78, 4915 (1983)] methods and a simple atom-atom model potential based on ab initio Hartree–Fock calculations and found that their cross sections agree fairly well with ours for collision energies above 500 cm−1, but that the inclusion of long range attractive dispersion interactions is crucial to obtain reliable cross sections at lower energies and rate coefficients at lower temperatures. [ABSTRACT FROM AUTHOR]

We study the electronic spin flux (atomic-scale flow of the spin density in molecules) by a perturbation analysis and ab initio nonadiabatic calculations. We derive a general perturbative expression of the charge and spin fluxes and identify the driving perturbation of the fluxes to be the time derivative of the electron-nucleus interaction term in the Hamiltonian. We then expand the expression in molecular orbitals so as to identify relevant components of the fluxes. Our perturbation theory describes the electronic fluxes in the early stage of reactions in an intuitively clear manner. The perturbation theory is then applied to an analysis of the spin flux obtained in ab initio calculations of the radical reaction of O2 and CH3· starting from three distinct spin configurations; (a) CH3· and triplet O2 with total spin of the system set S t o t = 1 / 2 (b) CH3· and singlet O2, S t o t = 1 / 2 , and (c) CH3· and triplet O2, S t o t = 3 / 2. Further analysis of the time-dependent behaviors of the spin flux in these numerical simulations reveals (i) the spin flux induces rearrangement of the local spin structure, such as reduction of the spin polarization arising from the triplet O2 and (ii) the spin flux flows from O2 to CH3· in the reaction starting from spin configuration (a) and from CH3· to O2 in that starting from configuration (b), whereas no major intermolecular spin flux was observed in that starting from configuration (c). Our study thus establishes the mechanism of the spin flux that rearranges the local spin structures associated with chemical bonds. [ABSTRACT FROM AUTHOR]

Optically active spin defects in semiconductors can serve as spin-to-photon interfaces, key components in quantum technologies. Silicon carbide (SiC) is a promising host of spin defects thanks to its wide bandgap and well-established crystal growth and device technologies. In this study, we investigated the oxygen-vacancy complexes as potential spin defects in SiC by means of ab initio calculations. We found that the OCVSi defect has a substantially low formation energy compared with its counterpart, OSiVC, regardless of the Fermi level position. The OCVSi defect is stable in its neutral charge state with a high-spin ground state (S = 1) within a wide energy range near the midgap energy. The zero-phonon line (ZPL) of the OCVSi0 defect lies in the near-infrared regime, 1.11–1.24 eV (1004–1117 nm). The radiative lifetime for the ZPL transition of the defect in kk configuration is fairly short (12.5 ns). Furthermore, the estimated Debye–Waller factor for the optical transition is 13.4%, indicating a large weight of ZPL in the photoluminescence spectrum. All together, we conclude that the OCVSi0 defect possesses desirable spin and optical properties and thus is potentially attractive as a quantum bit. [ABSTRACT FROM AUTHOR]

Predictive atomistic simulations are increasingly employed for data intensive high throughput studies that take advantage of constantly growing computational resources. To handle the sheer number of individual calculations that are needed in such studies, workflow management packages for atomistic simulations have been developed for a rapidly growing user base. These packages are predominantly designed to handle computationally heavy ab initio calculations, usually with a focus on data provenance and reproducibility. However, in related simulation communities, e.g., the developers of machine learning interatomic potentials (MLIPs), the computational requirements are somewhat different: the types, sizes, and numbers of computational tasks are more diverse and, therefore, require additional ways of parallelization and local or remote execution for optimal efficiency. In this work, we present the atomistic simulation and MLIP fitting workflow management package wfl and Python remote execution package ExPyRe to meet these requirements. With wfl and ExPyRe, versatile atomic simulation environment based workflows that perform diverse procedures can be written. This capability is based on a low-level developer-oriented framework, which can be utilized to construct high level functionality for user-friendly programs. Such high level capabilities to automate machine learning interatomic potential fitting procedures are already incorporated in wfl, which we use to showcase its capabilities in this work. We believe that wfl fills an important niche in several growing simulation communities and will aid the development of efficient custom computational tasks. [ABSTRACT FROM AUTHOR]

The hydrogen abstraction reaction of the cyano radical with molecules of ethane presents some interesting points in the chemistry from ultra-cold to combustion environments especially with regard to HCN(v) product vibrational distribution. In order to understand its dynamics, a new analytical full-dimensional potential energy surface was developed, named PES-2023. It uses a combination of valence bond and mechanic molecular terms as the functional form, fitted to high-level ab initio calculations at the explicitly correlated CCSD(T)-F12/aug-cc-pVTZ level on a reduced and selected number of points describing the reactive process. The new surface showed a continuous and smooth behavior, describing reasonably the topology of the reaction: high exothermicity, low barrier, and presence of intermediate complexes in the entrance and exit channels. Using quasi-classical trajectory calculations (QCT) on the new PES-2023, a dynamics study was performed at room temperature with special emphasis on the HCN(v1,v2,v3) product stretching and bending vibrational excitations, and the results were compared with the experimental evidence, which presented discrepancies in the bending excitation. The available energy was mostly deposited as HCN(v) vibrational energy with the vibrational population inverted in the CH stretching mode and not inverted in the CN stretching and bending modes, thus simulating the experimental evidence. Other dynamics properties at room temperature were also analyzed; cold rotational energy distribution was found, associated with a linear and soft transition state, and backward scattering distribution was found, associated with a rebound mechanism. [ABSTRACT FROM AUTHOR]

The effect of the presence of Ar on the isomerization reaction HCN ⇄ CNH is investigated via machine learning. After the potential energy surface function is developed based on the CCSD(T)/aug-cc-pVQZ level ab initio calculations, classical trajectory simulations are performed. Subsequently, with the aim of extracting insights into the reaction dynamics, the obtained reactivity, that is, whether the reaction occurs or not under a given initial condition, is learned as a function of the initial positions and momenta of all the atoms in the system. The prediction accuracy of the trained model is greater than 95%, indicating that machine learning captures the features of the phase space that affect reactivity. Machine learning models are shown to successfully reproduce reactivity boundaries without any prior knowledge of classical reaction dynamics theory. Subsequent analyses reveal that the Ar atom affects the reaction by displacing the effective saddle point. When the Ar atom is positioned close to the N atom (resp. the C atom), the saddle point shifts to the CNH (HCN) region, which disfavors the forward (backward) reaction. The results imply that analyses aided by machine learning are promising tools for enhancing the understanding of reaction dynamics. [ABSTRACT FROM AUTHOR]

Parity non-conservation (PNC) due to the weak interaction is predicted to give rise to enantiomer dependent vibrational constants in chiral molecules, but the phenomenon has so far eluded experimental observation. The enhanced sensitivity of molecules to physics beyond the Standard Model (BSM) has led to substantial advances in molecular precision spectroscopy, and these may be applied to PNC searches as well. Specifically, trapped molecular ion experiments leverage the universality of trapping charged particles to optimize the molecular ion species studied toward BSM searches, but in searches for PNC, only a few chiral molecular ion candidates have been proposed so far. Importantly, viable candidates need to be internally cold, and their internal state populations should be detectable with high quantum efficiency. To this end, we focus on molecular ions that can be created by near threshold resonant two-photon ionization and detected via state-selective photo-dissociation. Such candidates need to be stable in both charged and neutral chiral versions to be amenable to these methods. Here, we present a collection of suitable chiral molecular ion candidates we have found, including CHDBrI+ and CHCaBrI+, that fulfill these conditions according to our ab initio calculations. We find that organo-metallic species have low ionization energy as neutrals and relatively high dissociation thresholds. Finally, we compute the magnitude of the PNC values for vibrational transitions for some of these candidates. An experimental demonstration of state preparation and readout for these candidates will be an important milestone toward measuring PNC in chiral molecules for the first time. [ABSTRACT FROM AUTHOR]

The analysis and modeling of high-resolution spectra of nonrigid molecules require a specific Hamiltonian and group-theoretical formulation that differs significantly from that of more familiar rigid systems. Within the framework of Hougen–Bunker–Johns (HBJ) theory, this paper is devoted to the construction of a nonrigid Hamiltonian based on a suitable combination of numerical calculations for the nonrigid part in conjunction with the irreducible tensor operator method for the rigid part. For the first time, a variational calculation from ab initio potential energy surfaces is performed using the HBJ kinetic energy operator built from vibrational, large-amplitude motion, and rotational tensor operators expressed in terms of curvilinear and normal coordinates. Group theory for nonrigid molecules plays a central role in the characterization of the overall tunneling splittings and is discussed in the present approach. The construction of the dipole moment operator is also examined. Validation tests consisting of a careful convergence study of the energy levels as well as a comparison of results obtained from independent computer codes are given for the nonrigid molecules CH2, CH3, NH3, and H2O2. This work paves the way for the modeling of high-resolution spectra of larger nonrigid systems. [ABSTRACT FROM AUTHOR]

Catalyzed by enormous success in the industrial sector, many research programs have been exploring data-driven, machine learning approaches. Performance can be poor when the model is extrapolated to new regions of chemical space, e.g., new bonding types, new many-body interactions. Another important limitation is the spatial locality assumption in model architecture, and this limitation cannot be overcome with larger or more diverse datasets. The outlined challenges are primarily associated with the lack of electronic structure information in surrogate models such as interatomic potentials. Given the fast development of machine learning and computational chemistry methods, we expect some limitations of surrogate models to be addressed in the near future; nevertheless spatial locality assumption will likely remain a limiting factor for their transferability. Here, we suggest focusing on an equally important effort—design of physics-informed models that leverage the domain knowledge and employ machine learning only as a corrective tool. In the context of material science, we will focus on semi-empirical quantum mechanics, using machine learning to predict corrections to the reduced-order Hamiltonian model parameters. The resulting models are broadly applicable, retain the speed of semiempirical chemistry, and frequently achieve accuracy on par with much more expensive ab initio calculations. These early results indicate that future work, in which machine learning and quantum chemistry methods are developed jointly, may provide the best of all worlds for chemistry applications that demand both high accuracy and high numerical efficiency. [ABSTRACT FROM AUTHOR]

Vibrational spectra in the acetylenic and aromatic C–H stretching regions of phenylacetylene and fluorophenylacetylenes, viz., 2-fluorophenylacetylene, 3-fluorophenylacetylene, and 4-fluorophenylacetylene, were measured using the IR-UV double resonance spectroscopic method. The spectra, in both acetylenic and aromatic C–H stretching regions, were complex exhibiting multiple bands. Ab-initio anharmonic calculations with quartic potential using B97D3/6-311++G(d,p) and vibrational configuration interaction were able to capture all important spectral features in both the regions of the experimentally observed spectra for all four molecules considered in the present work. Interestingly, for phenylacetylene, the spectrum in the acetylenic C–H stretching region emerges due to anharmonic coupling of modes localized on the acetylenic moiety along with the other ring modes, which also involve displacements on the acetylenic group, which is in contrast to what has been proposed and propagated in the literature. In general, this coupling scheme is invariant to the fluorine atom substitution. For the aromatic C–H stretching region, the observed spectrum emerges due to the coupling of the C–H stretching with C–C stretching and C–H in-plane bending modes. [ABSTRACT FROM AUTHOR]

We present a novel method of modeling the contact between a metal and a two-dimensional semiconductor. Using Au on MoS 2 as an example, we self-consistently solve the Schrödinger and Poisson equations and obtain the charge density in the contact. We consider open boundary conditions using the quantum transmitting boundary method and model the electron current through the contact region. We then investigate the effect of effective Schottky barrier height, electrostatic doping, and length of the overlap region on the contact resistance in a top contact geometry. By using data from experiments or from ab initio calculations for the fitting of parameters, such as the effective Schottky barrier height, the model can be used to efficiently obtain the contact resistance and, therefore, the quality of the contact. Furthermore, we investigate the effect of sampling of the Brillouin zone in the transverse direction on the numerical calculation of key quantities, such as contact resistance and free charge density. Additionally, we show that the boundary conditions applied to the Poisson equation during the calculation of the free charge density have a significant impact on the calculated contact resistance and that the impact is more pronounced in heterostructures with a larger Schottky barrier. We found that the contact resistance may be significantly underestimated, by up to one order of magnitude, when the height of the simulation domain is not large enough. [ABSTRACT FROM AUTHOR]

Lithium cobalt oxide is a convenient model material for the vast family of cathode materials with a layered structure and still retains some commercial perspectives for microbatteries and some other applications. In this work, we have used ab initio calculations, x-ray diffraction, Raman spectroscopy, and a theoretical physical model, based on quasi-harmonic approximation with anharmonic contributions of the three-phonon and four-phonon processes, to study a temperature-induced change of Raman spectra for LiCoO2. The obtained values of shift and broadening for Eg and A1g bands can be used for quantitative characterization of temperature change, for example, due to laser-induced heating during Raman spectra measurements. The theoretical analysis of the experimental results lets us conclude that Raman spectra changes for LiCoO2 can be explained by the combination of thermal expansion of the crystal lattice and phonon damping by anharmonic coupling with comparable contributions of the three-phonon and four-phonon processes. The obtained results can be further used to develop Raman-based quality control tools. [ABSTRACT FROM AUTHOR]

High-accuracy prediction of the physical properties of amorphous materials is challenging in condensed-matter physics. A promising method to achieve this is machine-learning potentials, which is an alternative to computationally demanding ab initio calculations. When applying machine-learning potentials, the construction of descriptors to represent atomic configurations is crucial. These descriptors should be invariant to symmetry operations. Handcrafted representations using a smooth overlap of atomic positions and graph neural networks (GNN) are examples of methods used for constructing symmetry-invariant descriptors. In this study, we propose a novel descriptor based on a persistence diagram (PD), a two-dimensional representation of persistent homology (PH). First, we demonstrated that the normalized two-dimensional histogram obtained from PD could predict the average energy per atom of amorphous carbon at various densities, even when using a simple model. Second, an analysis of the dimensional reduction results of the descriptor spaces revealed that PH can be used to construct descriptors with characteristics similar to those of a latent space in a GNN. These results indicate that PH is a promising method for constructing descriptors suitable for machine-learning potentials without hyperparameter tuning and deep-learning techniques. [ABSTRACT FROM AUTHOR]

To unravel the structural, energetic stability, electronic, optical, excitonic, vibrational, and thermodynamic properties of monoclinic 1A'-OsO 2 monolayer, we employed the first-principles calculations based on density functional theory (DFT) within the generalized gradient approximation (GGA) and the HSE06 hybrid functional, considering the norm-conserved pseudopotentials, and a combination of a tight binding plus BSE (TB+BSE) approach for the analysis of optical and excitonic properties at IPA and BSE levels. Our simulations demonstrate that the 1A'-OsO 2 monolayer is a structurally and energetically stable semiconductor, and gives us a direct bandgap value, E(Γ → Γ), of 0.304, 0.254, and 1.119 eV, which were obtained through GGA-PBE, GGA-PBE+SOC, and HSE06-level of calculation, respectively. From the excitonic and optical properties, we observe that this system shows a large exciton binding energy of around 0.3 eV for the indirect ground state exciton, displaying an optical bandgap of 0.78 eV. We also show the use of light polarization as a mechanism to control the refractive index. The phonon dispersion and the infrared (IR) and Raman spectra were obtained, with its main peaks being assigned. Lastly, through thermodynamic potentials calculations, the Free energy (F) indicates that the synthesis of the 1A'-OsO 2 monolayer would be spontaneous even at low temperatures. All theses properties demonstrate that the 1A'-OsO 2 monolayer has potential applications in optoelectronic and thermal devices at the nanoscale. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics leading to the C–N bond cleavage in methylamine (CH3NH2) are investigated upon photoexcitation in the blue edge of the first absorption A-band, in the 198–204 nm range. Velocity map images of the generated methyl (CH3) fragment detected in specific vibrational modes, i.e., ν = 0, ν1 = 1, and ν2 = 1, through resonance enhanced multiphoton ionization, are presented along with the corresponding translational energy distributions and the angular analysis. The experimental results are complemented by high-level ab initio calculations of potential energy curves as a function of the C–N bond distance. While a similar single Boltzmann-type contribution is observed in all the translational energy distributions measured, the speed-dependent anisotropy parameter obtained through the angular analysis reveals the presence of two different mechanisms. Prompt dissociation through the conical intersection between the A ̃ 1 A ′ first excited state and the ground state located in the exit channel is, indeed, revealed as a minor channel. In contrast, slow dissociation on the ground state, presumably from frustrated N–H bond cleavage trajectories, constitutes the major reaction pathway leading to the methyl formation. [ABSTRACT FROM AUTHOR]

With the motivation of searching for new superconductors with better hardness in the Th–B system, we have performed ab initio evolutionary searches for all the stable compounds in this binary system in the pressure range of 0–200 GPa. From our enthalpy of formation calculations, it is found that only ThB4 (Space group No. P4/mbm), ThB6 (Space group No. P m 3 ¯ m), and ThB12 (Space group No. F m 3 ¯ m) compositions are preferred at zero pressure, in accordance with the experimental reports. Under pressure, our calculations predict the thermodynamically stable compositions, ThB (Space group No. R 3 ¯ m), Th3B4 (Space group No. R 3 ¯ m), ThB2 (Space group No. Amm2), and ThB8 (Space group No. R 3 ¯ m) at 54, 19, 35, and 51 GPa, respectively. Furthermore, although the thermodynamical stability of these compounds is predicted to be at high pressures, the possibility of occurrence at 0 GPa due to metastability still exists. The detailed calculations and analysis of the electronic structure and mechanical and thermal properties have been carried out on these materials using the ab initio tool. The P4/mbm phase of ThB4 and the F m 3 ¯ m phase of ThB12 exhibit high hardness of 30.5 and 35.2 GPa under ambient conditions, which is comparable the hard material, B4C. On the other hand, among all the thorium borides, ThB2 shows a high electron–phonon coupling constant of 0.804 and is predicted to have Tc around 12.72 K. In addition, it has been found that the predicted high-pressure compositions, Th3B4 and ThB, display superconductive behavior under pressure. Additionally, various thermophysical quantities such as lattice thermal conductivity, bulk modulus, thermal expansion coefficient, specific heat capacity, and Gibbs free energy under ambient conditions have been determined from these calculations. [ABSTRACT FROM AUTHOR]

The possible existence of a liquid–liquid critical point in deeply supercooled water has been a subject of debate due to the challenges associated with providing definitive experimental evidence. The pioneering work by Mishima and Stanley [Nature 392, 164–168 (1998)] sought to shed light on this problem by studying the melting curves of different ice polymorphs and their metastable continuation in the vicinity of the expected liquid–liquid transition and its associated critical point. Based on the continuous or discontinuous changes in the slope of the melting curves, Mishima [Phys. Rev. Lett. 85, 334 (2000)] suggested that the liquid–liquid critical point lies between the melting curves of ice III and ice V. We explore this conjecture using molecular dynamics simulations with a machine learning model based on ab initio quantum-mechanical calculations. We study the melting curves of ices III, IV, V, VI, and XIII and find that all of them are supercritical and do not intersect the liquid–liquid transition locus. We also find a pronounced, yet continuous, change in the slope of the melting lines upon crossing of the liquid locus of maximum compressibility. Finally, we analyze the literature in light of our findings and conclude that the scenario in which the melting curves are supercritical is favored by the most recent computational and experimental evidence. Although the preponderance of evidence is consistent with the existence of a second critical point in water, the behavior of ice polymorph melting lines does not provide strong evidence in support of this viewpoint, according to our calculations. [ABSTRACT FROM AUTHOR]

The effects of in-plane strain on the dielectric constant of the Be0.25Mg0.75O rock salt superlattice are investigated through ab initio thermodynamics calculations. Based on a previous report that the long apical Be–O bond increased the dielectric constant, the in-plane compressive strain dielectric constant is expected to increase the dielectric constant. Unlike the zero-strain case, the apical Mg–O bonds also contribute to the increase in the dielectric constant under compressive strain. However, small Be ions tend to occupy narrow spaces in the MgO-based rock salt structure, which can lead to an increase in dielectric constant even under in-plane tensile strain, depending on the local position of Be ions and its interaction with O ions. At higher temperatures, several configurations under strain showed a significant increase in the dielectric constant due to the elongation of the apical Be–O bond. Considering temperature and strain comprehensively, this study suggests that the Be0.25MgO0.75O superlattice under −2% in-plane compressive strain could be a promising candidate structure for achieving a high-κ value of approximately 30. [ABSTRACT FROM AUTHOR]

The equilibrium structure of selenophenol has been investigated using rotational spectroscopy and high-level quantum mechanical calculations, offering electronic and structural insight into the scarcely studied selenium compounds. The jet-cooled broadband microwave spectrum was measured in the 2–8 GHz cm-wave region using broadband (chirped-pulse) fast-passage techniques. Additional measurements up to 18 GHz used narrow-band impulse excitation. Spectral signatures were obtained for six isotopic species of selenium (80Se, 78Se, 76Se, 82Se, 77Se, and 74Se), together with different monosubstituted 13C species. The (unsplit) rotational transitions associated with the non-inverting μa-dipole selection rules could be partially reproduced with a semirigid rotor model. However, the internal rotation barrier of the selenol group splits the vibrational ground state into two subtorsional levels, doubling the dipole-inverting μb transitions. The simulation of the double-minimum internal rotation gives a very low barrier height (B3PW91: 42 cm−1), much smaller than for thiophenol (277 cm−1). A monodimensional Hamiltonian then predicts a huge vibrational separation of 72.2 GHz, justifying the non-observation of μb transitions in our frequency range. The experimental rotational parameters were compared with different MP2 and density functional theory calculations. The equilibrium structure was determined using several high-level ab initio calculations. A final Born–Oppenheimer ( r e BO ) structure was obtained at the coupled-cluster CCSD(T)_ae/cc-wCVTZ level of theory, including small corrections for the wCVTZ → wCVQZ basis set enlargement calculated at the MP2 level. The mass-dependent method with predicates was used to produce an alternative r m (2) structure. The comparison between the two methods confirms the high accuracy of the r e BO structure and offers information on other chalcogen-containing molecules. [ABSTRACT FROM AUTHOR]

This paper presents results of a comprehensive study from first principles into the properties of Ni, Pd, Rh, and Ir crystals under pressure. We calculated elastic constants, phonon spectra, isotherms, Hugoniots, sound velocities, relative structural stability, and phase diagrams. It is shown that in nickel and palladium under high pressures (>0.14 TPa) and temperatures (>4 kK), the body-centered cubic structure is thermodynamically most stable than of the face-centered cubic one. Calculated results suggest that nickel under Earth-core conditions (P ∼ 0.3 TPa, T ∼ 6 kK) have a bcc structure. No structural changes were found to occur in Rh and Ir under pressures to 1 TPa at least. This paper also provides estimations for the pressure and temperature at which the metals of interest begin to melt under shock compression. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of methylamine (CH3NH2) upon excitation in the blue edge of the first absorption A-band, in the 198–203 nm range, are investigated by means of nanosecond pump–probe laser pulses and velocity map imaging combined with H(2S)-atom detection through resonance enhanced multiphoton ionization. The images and corresponding translational energy distributions for the H-atoms produced show three different contributions associated with three reaction pathways. The experimental results are complemented by high-level ab initio calculations. The potential energy curves computed as a function of the N–H and C–H bond distances allow us to draw a picture of the different mechanisms. Major dissociation occurs through N–H bond cleavage and it is triggered by an initial geometrical change, i.e., from a pyramidal configuration of the C–NH2 with respect to the N atom to a planar geometry. The molecule is then driven into a conical intersection (CI) seam where three outcomes can take place: first, threshold dissociation into the second dissociation limit, associated with the formation of CH3NH ( A ̃) , is observed; second, direct dissociation after passage through the CI leading to the formation of ground state products; and third, internal conversion into the ground state well in advance to dissociation. While the two last pathways were previously reported at a variety of wavelengths in the 203–240 nm range, the former had not been observed before to the best of our knowledge. The role of the CI and the presence of an exit barrier in the excited state, which modify the dynamics leading the two last mechanisms, are discussed considering the different excitation energies used. [ABSTRACT FROM AUTHOR]

Circuit depth reduction is of critical importance for quantum chemistry simulations on current and near term quantum computers. This issue is tackled by introducing a chemically aware strategy for the unitary coupled cluster ansatz. The objective is to use the chemical description of a system to aid in the synthesis of a quantum circuit. We combine this approach with two flavors of symmetry verification for the reduction of experimental noise. These methods enable the use of Quantinuum's System Model H1 ion trap quantum computer for a 6-qubit quantum subspace expansion calculation. We present (i) calculations to obtain methane's optical spectra; (ii) an atmospheric gas reaction simulation involving [ C H 3 ⋅ —H—OH]‡. Using our chemically aware unitary coupled cluster state-preparation strategy in tandem with state of the art symmetry verification methods, we improve device yield for CH4 at 6 qubits. This is demonstrated by a 90% improvement in two-qubit gate count and a reduction in relative error to 0.2% for electronic energy calculated on System Model H1. [ABSTRACT FROM AUTHOR]