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Glass and crystal are inherently different material states in terms of their structural and physical features; consequently, the direct quantitative connection between crystal and glass is lacking. Herein, we first show that the liquid fragility m, which is featured by the negative departure degree of viscosity with the temperature at the glass transition temperature (Tg), has a direct exponential correlation with the ratio of the average longest metal–oxygen and the average phosphorus, silicon, or boron–oxygen bond lengths of the crystal in various oxides including phosphates, silicates, and borates. Such a result can be rationalized by the fact that the fragility m in these glass-formers is associated with the total network rigidity determined by the weakest bond due to the "bucket effect" and the bond pair inheritance of glass from that of the crystal. Our work connects direct features between glass and crystal with identical composition, providing a new viewpoint bridging glass and crystal. [ABSTRACT FROM AUTHOR]

A linear chain of N particles connected by Morse bonds with periodic boundaries in a Brownian bath is considered as a model for polymer fracture. The potential of mean force (pomf) with respect to the length of a bond and its energy and entropic components are computed via Langevin Dynamics simulations at various chain elongations λ > 1. A narrow range of λ values is identified over which equilibrium is established between an intact (i) and a fractured (f) state over a pomf barrier. While the barrier and (f) regions of the pomf are well described by a well-known (N − 1)-bond adiabatic approximation, the shape of the (i) region departs from it, exhibiting a bimodal character. A new, 1-bond adiabatic approximation is proposed to explain this. The lower envelope of the two adiabatic approximations provides an excellent description of the pomf. The relationship between (f) states for individual bonds and for the entire chain is elucidated. A new approach, based on analysis of equilibrium tension autocorrelation functions, is developed to extract rate constants for the fracture and reformation of the chain in dependence of λ. Results from it agree with tension relaxation during nonequilibrium simulations initiated at equispaced configurations of the particles. Rate constants for chain fracture conform to a Boltzmann–Arrhenius–Zhurkov dependence on the tension averaged over the intact state of the chain, the activation length being higher than estimated from pomf extrema. These findings constitute a step toward a predictive multiscale simulation scheme for fracture in polymeric materials. [ABSTRACT FROM AUTHOR]

The coupled structural and electronic parameters of intramolecular hydrogen bonding play an important role in ultrafast chemical reactions, such as proton transfer processes. We perform one- and two-dimensional vibrational–electronic (1D and 2D VE) spectroscopy experiments to understand the couplings between vibrational and electronic coordinates in 10-Hydroxybenzo[h]quinoline, an ultrafast proton transfer system. The experiments reveal that the OH stretch (νOH) is strongly coupled to the electronic excitation, and Fourier analysis of the 1D data shows coherent oscillations from the low frequency backbone vibrational modes coupled to the νOH mode, resulting in an electronically detected vibronic signal. In-plane low-frequency vibrations at 242 and 386 cm−1 change the hydrogen bond distance and modulate the observed electronic signal in the polarization-selective 1D VE experiment through orientation-dependent coupling with the νOH mode. Resolution of the excitation frequency axis with 2D VE experiments reveals that excitation frequency, detection frequency, and experimental delay affect the frequency and strength of the vibronic transitions observed. Our results demonstrate evidence of direct coupling of the high frequency νOH mode with the S1 ← S0 electronic transition in 10-Hydroxybenzo[h]quinoline (HBQ), and orientation-dependent couplings of the low-frequency 242 and 386 cm−1 modes to the νOH mode and the electronic transition. This demonstration of multidimensional VE spectroscopy on HBQ reveals the potential of using 1D and 2D VE spectroscopy to develop a quantitative understanding of the role of vibronic coupling in hydrogen bonding and ultrafast proton transfer for complex systems. [ABSTRACT FROM AUTHOR]

Carbonyl groups (C=O) play crucial roles in the photophysics and photochemistry of biological systems. O1s x-ray photoelectron spectroscopy allows for targeted investigation of the C=O group, and the coupling between C=O vibration and O1s ionization is reflected in the fine structures. To elucidate its characteristic vibronic features, systematic Franck–Condon simulations were conducted for six common biomolecules, including three purines (xanthine, caffeine, and hypoxanthine) and three pyrimidines (thymine, 5F-uracil, and uracil). The complexity of simulation for these biomolecules lies in accounting for temperature effects and potential tautomeric variations. We combined the time-dependent and time-independent methods to efficiently account for the temperature effects and to provide explicit assignments, respectively. For hypoxanthine, the tautomeric effect was considered by incorporating the Boltzmann population ratios of two tautomers. The simulations demonstrated good agreement with experimental spectra, enabling differentiation of two types of carbonyl oxygens with subtle local structural differences, positioned between two nitrogens (O1) or between one carbon and one nitrogen (O2). The analysis provided insights into the coupling between C=O vibration and O1s ionization, consistently showing an elongation of the C=O bond length (by 0.08–0.09 Å) upon O1s ionization. [ABSTRACT FROM AUTHOR]

Based upon global-minimum searches and first-principles electronic structural calculations, we present the perfectly planar B6O50/−/2− (1–3) systems. Notably, the C2v B6O50/− (1–2) clusters mark a groundbreaking advancement as the first boron oxide clusters to feature a five-membered ring. Both structures exhibit remarkable similarity, each characterized by a central B3O2 ring surrounded by three terminal BO groups. However, a notable difference lies in the bond lengths within the B3O2 core, which are uniform in the former but uneven in the latter. Detailed canonical molecular orbital and AdNDP analyses reveal the delocalized π bonds over the B3O2 ring, affirming the π aromaticity of B6O5−. The Cs B6O52− (3) cluster showcases a chain-like arrangement with three terminal BO groups and a typical OBO group linked to a B2 core, emphasizing the crucial role of electrons in shaping the structure. Detailed chemical bonding analyses reveal the presence of dual three-center four-electron (3c–4e) π hyperbonds in 3, shedding further light on its unique bonding characteristics. Moreover, this study comprehensively extends the B(BO)n0/− (n = 1–5) series and provides valuable perspectives on their structural evolution. [ABSTRACT FROM AUTHOR]

We present an efficient first-principles based method geared toward reliably predicting the structures of solid materials across the Periodic Table. To this end, we use a density functional theory baseline with a compact, near-minimal min+s basis set, yielding low computational costs and memory demands. Since the use of such a small basis set leads to systematic errors in chemical bond lengths, we develop a linear pairwise correction, available for elements Z = 1–86 (excluding the lanthanide series), parameterized for use with the Perdew–Burke–Ernzerhof exchange–correlation functional. We demonstrate the reliability of this corrected approach for equilibrium volumes across the Periodic Table and the transferability to differently coordinated environments and multi-elemental crystals. We examine relative energies, forces, and stresses in geometry optimizations and molecular dynamics simulations. [ABSTRACT FROM AUTHOR]

A new computational framework for spinor-based relativistic exact two-component (X2C) calculations is developed using contracted basis sets with a spin–orbit contraction scheme. Generally contracted, j-adapted basis sets of p-block elements using primitive functions in the correlation-consistent basis sets are constructed for the X2C Hamiltonian with atomic mean-field spin–orbit integrals (the X2CAMF scheme). The contraction coefficients are taken from atomic X2CAMF Hartree–Fock spinors, thereby following the simple concept of a linear combination of atomic orbitals. Benchmark calculations of spin–orbit splittings, equilibrium bond lengths, and harmonic vibrational frequencies demonstrate the accuracy and efficacy of the j-adapted spin–orbit contraction scheme. [ABSTRACT FROM AUTHOR]

Photoexcitation is a powerful way to induce phase transition of strongly correlated materials and dynamically control terahertz (THz) devices integrated with photoinduced phase transition (PIPT) materials. To clarify controversies over the physical mechanism between electronic insulator-metal transition (IMT) and structural phase transition (SPT) of photoexcited vanadium dioxide (VO 2), the underlying atomic and electronic state changes during photoinduced monoclinic-to-rutile phase transition are illustrated, and the separation with different thresholds between the quasi-instantaneous IMT and the ultrafast SPT is discovered. Below the SPT threshold, there exist metastable states exhibiting the metal-like monoclinic phases, i.e., the strongest metallicity and weak monoclinic phases, when the bond lengths of the V–V pairs are closest. By analyzing the electronic transport properties of these metal-like monoclinic phases, the THz response of the whole phase transition process can be characterized for first time through the quantum-electromagnetic dispersion modeling method. The THz properties of the practical VO 2 film are simulated and the great alignments between the measurements and the simulations verify the proposed analysis method, which provides a powerful exploration path and insights for the theoretical analysis and design verification of PIPT materials and their optoelectronic THz devices. [ABSTRACT FROM AUTHOR]

Photoexcitation is a powerful way to induce phase transition of strongly correlated materials and dynamically control terahertz (THz) devices integrated with photoinduced phase transition (PIPT) materials. To clarify controversies over the physical mechanism between electronic insulator-metal transition (IMT) and structural phase transition (SPT) of photoexcited vanadium dioxide (VO 2), the underlying atomic and electronic state changes during photoinduced monoclinic-to-rutile phase transition are illustrated, and the separation with different thresholds between the quasi-instantaneous IMT and the ultrafast SPT is discovered. Below the SPT threshold, there exist metastable states exhibiting the metal-like monoclinic phases, i.e., the strongest metallicity and weak monoclinic phases, when the bond lengths of the V–V pairs are closest. By analyzing the electronic transport properties of these metal-like monoclinic phases, the THz response of the whole phase transition process can be characterized for first time through the quantum-electromagnetic dispersion modeling method. The THz properties of the practical VO 2 film are simulated and the great alignments between the measurements and the simulations verify the proposed analysis method, which provides a powerful exploration path and insights for the theoretical analysis and design verification of PIPT materials and their optoelectronic THz devices. [ABSTRACT FROM AUTHOR]

The spectrum of localized hole states (traps) in amorphous silicon nitride, a-Si3N4, is experimentally studied using the method of thermally stimulated depolarization. The experiment is compared with theoretical calculations using three models of the energy spectrum of traps: discrete spectrum (monoenergetic trap), continuous spectrum, and Gaussian trap distribution. The experiment is quantitatively described by a model of a discrete spectrum of traps with an energy of 1.15 eV and a width of no more than 0.01 eV. In the case of a continuous and Gaussian spectrum of traps, the contribution to depolarization is made by the deepest traps. The blurring of the trap energy level in a-Si3N4 due to the absence of long-range order (fluctuations in the Si–N bond length and fluctuations in the N–Si–N and Si–N–Si angles) does not exceed 0.01 eV. [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]

This article investigates the relaxation dynamics of the ionized 2a1 state of a water molecule within a water dimer. The study was motivated by findings from two previous pieces of research that focused on the relaxation behaviors of the inner-valence ionized water dimer. The present study discloses an observation indicating that water dimers display specific fragmentation patterns following inner-valence ionization, depending on the position of the vacancy. Vacancies were created in the 2a1 state of the proton-donating water molecule (PDWM) and proton-accepting water molecule (PAWM). Utilizing Born–Oppenheimer molecular dynamics simulations, the propagation of the 2a1 ionized state was carried out for both scenarios. The results revealed proton transfer occurred when the vacancy resided in the PDWM, accompanied by the closing of decay channels for O–H bond distance (RO–H) > 1.187 Å (matching Richter et al.'s findings). Conversely, when vacancy was on PAWM, we observed no closing of decay channels (aligning with Jahnke et al.'s findings). This difference translates to distinct fragmentation pathways. In PDWM cases, 2a1 state ionization leads to H3O+ −OH• formation. In contrast, PAWM vacancies result in decay pathways leading to H2O+–H2O+ products. [ABSTRACT FROM AUTHOR]

We optimize the internuclear geometry and electronic structure of a model chiral system to achieve a maximal photoelectron circular dichroism (PECD) in its one-photon ionization by circularly polarized light. The electronic structure calculations are performed by the single center method, while the optimization is done using quantum alchemy employing a Taylor series expansion. Thereby, the effect of bond lengths and uncompensated charge distributions on the chiral response of the model is investigated theoretically in some detail. It is demonstrated that manipulating a chiral asymmetry of the ionic potential may enhance the dichroic parameter (i.e., the PECD) of the randomly oriented model system well beyond β1 = 25%. Furthermore, we demonstrate that quantum alchemy is applicable to PECD despite the unusually strong coupling of spatial and electronic degrees of freedom and discuss the relative impact of the individual degrees of freedom in this model system. We define the necessary conditions for the computational design of PECD for real (non-model) chiral molecules using our approach. [ABSTRACT FROM AUTHOR]

We propose a novel implementation of the extended-dynamics equations for isothermal–isobaric ensemble in molecular dynamics, as the Martyna–Tobias–Klein thermostat and barostat. This method is suitable for systems with constraints and the Verlet-family integrators. Instead of iterations or the Trotter-expansion-based methods, both velocities and box sizes (scaling of bond lengths) are predicted. The algorithm begins with force calculation, requiring neither quarter nor half time steps, and necessitating iterations only inside SHAKE. Several tests demonstrate that the quality is comparable to other implementations. It is found that the formula relating the extended barostat mass to the characteristic time of volume fluctuations is inaccurate for condensed systems, which has consequences for the parameter setup. Emphasis is also put on the verification of the precise isothermal–isobaric ensemble and finite-size effects. [ABSTRACT FROM AUTHOR]

The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C–O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds. [ABSTRACT FROM AUTHOR]

Density functional approximations to the exchange–correlation energy can often identify strongly correlated systems and estimate their energetics through energy-minimizing symmetry-breaking. In particular, the binding energy curve of the strongly correlated chromium dimer is described qualitatively by the local spin density approximation (LSDA) and almost quantitatively by the Perdew–Burke–Ernzerhof generalized gradient approximation (PBE-GGA), where the symmetry breaking is antiferromagnetic for both. Here, we show that a full Perdew–Zunger self-interaction-correction (SIC) to LSDA seems to go too far by creating an unphysical symmetry-broken state, with effectively zero magnetic moment but non-zero spin density on each atom, which lies ∼4 eV below the antiferromagnetic solution. A similar symmetry-breaking, observed in the atom, better corresponds to the 3d↑↑4s↑3d↓↓4s↓ configuration than to the standard 3d↑↑↑↑↑4s↑. For this new solution, the total energy of the dimer at its observed bond length is higher than that of the separated atoms. These results can be regarded as qualitative evidence that the SIC needs to be scaled down in many-electron regions. [ABSTRACT FROM AUTHOR]

The structure of grain boundaries (GBs) of metals is essential in determining the solute segregation at GBs; however, its complexity prohibits the understanding of the underlying mechanism. We propose a geometric descriptor of GB segregation based on the non-local coordination number of cut surfaces from GBs, which determines the segregation energies of solutes at the grain boundaries of metals across multidimensional GB space, different solutes, and different matrices. The effectiveness of the descriptor originates from the correlation between bonding strength, d-band width, and coordination number. This descriptor only depends on the bond length and angle of pre-segregation sites at GBs and can be readily used for description and prediction. Our scheme builds a novel picture for understanding the role of GB structures in segregation and provides a useful tool for the design of advanced alloys. [ABSTRACT FROM AUTHOR]

VO2 is renowned for its electric transition from an insulating monoclinic (M1) phase, characterized by V–V dimerized structures, to a metallic rutile (R) phase above 340 K. This transition is accompanied by a magnetic change: the M1 phase exhibits a non-magnetic spin-singlet state, while the R phase exhibits a state with local magnetic moments. Simultaneous simulation of the structural, electric, and magnetic properties of this compound is of fundamental importance, but the M1 phase alone has posed a significant challenge to the density functional theory (DFT). In this study, we show none of the commonly used DFT functionals, including those combined with on-site Hubbard U to treat 3d electrons better, can accurately predict the V–V dimer length. The spin-restricted method tends to overestimate the strength of the V–V bonds, resulting in a small V–V bond length. Conversely, the spin-symmetry-breaking method exhibits the opposite trends. Each of these two bond-calculation methods underscores one of the two contentious mechanisms, i.e., Peierls lattice distortion or Mott localization due to electron–electron repulsion, involved in the metal–insulator transition in VO2. To elucidate the challenges encountered in DFT, we also employ an effective Hamiltonian that integrates one-dimensional magnetic sites, thereby revealing the inherent difficulties linked with the DFT computations. [ABSTRACT FROM AUTHOR]

VO2 is renowned for its electric transition from an insulating monoclinic (M1) phase, characterized by V–V dimerized structures, to a metallic rutile (R) phase above 340 K. This transition is accompanied by a magnetic change: the M1 phase exhibits a non-magnetic spin-singlet state, while the R phase exhibits a state with local magnetic moments. Simultaneous simulation of the structural, electric, and magnetic properties of this compound is of fundamental importance, but the M1 phase alone has posed a significant challenge to the density functional theory (DFT). In this study, we show none of the commonly used DFT functionals, including those combined with on-site Hubbard U to treat 3d electrons better, can accurately predict the V–V dimer length. The spin-restricted method tends to overestimate the strength of the V–V bonds, resulting in a small V–V bond length. Conversely, the spin-symmetry-breaking method exhibits the opposite trends. Each of these two bond-calculation methods underscores one of the two contentious mechanisms, i.e., Peierls lattice distortion or Mott localization due to electron–electron repulsion, involved in the metal–insulator transition in VO2. To elucidate the challenges encountered in DFT, we also employ an effective Hamiltonian that integrates one-dimensional magnetic sites, thereby revealing the inherent difficulties linked with the DFT computations. [ABSTRACT FROM AUTHOR]

Molecular-level nucleation has not been clearly understood due to the complexity of multi-body potentials and the stochastic, rare nature of the process. This work utilizes molecular dynamics (MD) simulations, incorporating a first-principles-based deep neural network (DNN) potential model, to investigate homogeneous water vapor condensation. The nucleation rates and critical nucleus sizes predicted by the DNN model are compared against commonly used semi-empirical models, namely extended simple point charge (SPC/E), TIP4P, and OPC, in addition to classical nucleation theory (CNT). The nucleation rates from the DNN model are comparable with those from the OPC model yet surpass the rates from the SPC/E and TIP4P models, a discrepancy that could mainly arise from the overestimated bulk free energy by SPC/E and TIP4P. The surface free energy predicted by CNT is lower than that in MD simulations, while its bulk free energy is higher than that in MD simulations, irrespective of the potential model used. Further analysis of cluster properties with the DNN model unveils pronounced variations of O–H bond length and H–O–H bond angle, along with averaged bond lengths and angles that are enlarged during embryonic cluster formation. Properties such as cluster surface free energy and liquid-to-vapor density transition profiles exhibit significant deviations from CNT assumptions. [ABSTRACT FROM AUTHOR]

The theory of analytic gradients is presented for the projector-based density functional theory (DFT) embedding approach utilizing the Huzinaga-equation. The advantages of the Huzinaga-equation-based formulation are demonstrated. In particular, it is shown that the projector employed does not appear in the Lagrangian, and the potential risk of numerical problems is avoided at the evaluation of the gradients. The efficient implementation of the analytic gradient theory is presented for approaches where hybrid DFT, second-order Møller–Plesset perturbation theory, or double hybrid DFT are embedded in lower-level DFT environments. To demonstrate the applicability of the method and to gain insight into its accuracy, it is applied to equilibrium geometry optimizations, transition state searches, and potential energy surface scans. Our results show that bond lengths and angles converge rapidly with the size of the embedded system. While providing structural parameters close to high-level quality for the embedded atoms, the embedding approach has the potential to relax the coordinates of the environment as well. Our demonstrations on a 171-atom zeolite and a 570-atom protein system show that the Huzinaga-equation-based embedding can accelerate (double) hybrid gradient computations by an order of magnitude with sufficient active regions and enables affordable force evaluations or geometry optimizations for molecules of hundreds of atoms. [ABSTRACT FROM AUTHOR]

The energetic stability of positron–dianion systems [A−; e+; A−] is studied via many-body theory, where A− includes H−, F−, Cl−, and the molecular anions (CN)− and (NCO)−. Specifically, the energy of the system as a function of ionic separation is determined by solving the Dyson equation for the positron in the field of the two anions using a positron–anion self-energy as constructed in Hofierka et al. [Nature 606, 688 (2022)] that accounts for correlations, including polarization, screening, and virtual-positronium formation. Calculations are performed for a positron interacting with H 2 2 − , F 2 2 − , and Cl 2 2 − and are found to be in good agreement with previous theory. In particular, we confirm the presence of two minima in the potential energy of the [H−; e+; H−] system with respect to ionic separation: a positronically bonded [H−; e+; H−] local minimum at ionic separations r ∼ 3.4 Å and a global minimum at smaller ionic separations r ≲ 1.6 Å that gives overall instability of the system with respect to dissociation into a H2 molecule and a positronium negative ion, Ps−. The first predictions are made for positronic bonding in dianions consisting of molecular anionic fragments, specifically for (CN) 2 2 − and (NCO) 2 2 − . In all cases, we find that the molecules formed by the creation of a positronic bond are stable relative to dissociation into A− and e+A− (positron bound to a single anion), with bond energies on the order of 1 eV and bond lengths on the order of several ångstroms. [ABSTRACT FROM AUTHOR]

31P nuclear magnetic resonance (NMR) chemical shifts were shown to be very sensitive to the basis set used at the geometry optimization stage. Commonly used energy-optimized basis sets for a phosphorus atom containing only one polarization d-function were shown to be unable to provide correct equilibrium geometries for the calculations of phosphorus chemical shifts. The use of basis sets with at least two polarization d-functions on a phosphorus atom is strongly recommended. In this paper, an idea of creating the basis sets purposed for the geometry optimization that provide the least possible error coming from the geometry factor of accuracy in the resultant NMR shielding constants is proposed. The property-energy consisted algorithm with the target function in the form of the molecular energy gradient relative to P–P bond lengths was applied to create new geometry-oriented pecG-n (n = 1, 2) basis sets for a phosphorus atom. New basis sets have demonstrated by far superior performance as compared to the other commonly used energy-optimized basis sets in massive calculations of 31P NMR chemical shifts carried out at the gauge-including atomic orbital-coupled cluster singles and doubles/pecS-2 level of the theory by taking into account solvent, vibrational, and relativistic corrections. [ABSTRACT FROM AUTHOR]

The correlation consistent basis sets (cc-pVnZ with n = D, T, Q, 5) for the Ga–Br elements have been redesigned, tuning the sets for use for density functional approximations. Steps to redesign these basis sets for an improved correlation energy recovery and efficiency include truncation of higher angular momentum functions, recontraction of basis set coefficients, and reoptimization of basis set exponents. These redesigned basis sets are compared with conventional cc-pVnZ basis sets and other basis sets, which are, in principle, designed to achieve systematic improvement with respect to increasing basis set size. The convergence of atomic energies, bond lengths, bond dissociation energies, and enthalpies of formation to the Kohn–Sham limit is improved relative to other basis sets where convergence to the Kohn–Sham limit is typically not observed. [ABSTRACT FROM AUTHOR]

Experimental findings by others suggest that OH radicals are formed in unexpected abundance on or near surfaces of 1–50 µm microdroplets comprised of pure water, but the mechanism by which these radicals are generated is not yet fully resolved. In this work, we examine two possibilities using ab initio electronic structure methods: (1) electron transfer (ET) from a microdroplet surface-bound OH− anion to a nearby H3O+ cation and (2) proton transfer (PT) from such a H3O+ cation to a nearby OH− anion. Our findings suggest that both processes are possible but only if the droplet's underlying water molecules comprising the microdroplet provide little screening of the Coulomb interaction between the anion and cation once they reach ∼10 Å of one another. In the ET event, an OH radical is formed directly; for PT, the OH formation occurs because the new O–H bond formed by the transferred proton is created at a bond length sufficiently elongated to permit homolytic cleavage. Both the ET and PT pathways predict that H atoms will also be formed. Finally, we discuss the roles played by strong local electric fields in mechanisms that have previously been proposed and that occur in our two mechanisms. [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]

π-conjugated polymers have been used in a wide range of practical applications, partly due to their unique properties that originate in the delocalization of electrons through the polymer backbone. The level of delocalization can be characterized by the induced bond length alternation (BLA), with shorter BLA connected with strong delocalization and vice versa. The accurate description of this structural parameter can be considered a benchmark for testing the capability of different electronic structure methods for self-interaction error (SIE) removal and electron correlation inclusion. Density functional theory (DFT), in its local or semi-local flavors, suffers from SIE and, thus, underestimates the BLA compared to self-interaction-free methods. In this work, we utilize the Fermi–Löwdin orbital self-interaction correction (FLOSIC) method for one-electron self-interaction removal to characterize the BLA of five oligomers with increasing length extrapolated to the polymeric limit. We compare the self-interaction-free BLA to several DFT approximations, Møller–Plesset second-order perturbation theory (MP2), and the BLA obtained with the domain based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] approximation. Our findings show that FLOSIC corrects for the small BLA given by (semi-)local DFT approximations, but it tends to overcorrect with respect to CAM-B3LYP, MP2, and DLPNO-CCSD(T). [ABSTRACT FROM AUTHOR]

Pseudopotentials (PP) are extensively used in electronic structure calculations, particularly for molecules containing heavy elements. Parameters in PPs are mainly determined from ab initio results, and errors of such PPs in density functional theory (DFT) calculations have been studied previously. However, PP errors on results with spin–orbit coupling and those in time-dependent DFT (TDDFT) calculations have not been reported previously. In this work, we investigate the error of the small-core energy-consistent Stuttgart/Koln pseudopotentials in DFT and TDDFT calculations with and without spin–orbit coupling. Ground state bond lengths, harmonic frequencies, dissociation energies, and vertical excitation energies for a series of closed-shell diatomic heavy and superheavy p-block molecules are calculated using several popular exchange-correlation functionals. PP errors are estimated by comparing with results using the all-electron Dirac–Coulomb (-Gaunt) Hamiltonian. Our results show that the difference between ground state properties and most excitation energies in scalar-relativistic calculations with the PP and those of all-electron calculations is quite small. This difference becomes somewhat larger when spin–orbit coupling (SOC) is present, especially for properties that are affected by SOC to some extent. In addition, the errors of the PPs are insensitive to the employed exchange-correlation functionals in most cases. Our results indicate that reasonable DFT and TDDFT results can be obtained using the small-core energy-consistent Stuttgart/Koln pseudopotentials for heavy and super-heavy p-block molecules. [ABSTRACT FROM AUTHOR]

Motivated by the recent experimental study on hydrogen storage in MXene multilayers [Liu et al., Nat. Nanotechnol. 16, 331 (2021)], for the first time we propose a workflow to computationally screen 23 857 compounds of MXene to explore the general relation between the activated H2 bond length and adsorption distance. By using density functional theory we generate a dataset to investigate the adsorption geometries of hydrogen on MXenes, based on which we train physics-informed atomistic line graph neural networks (ALIGNNs) to predict adsorption parameters. To fit the results, we further derived a formula that quantitatively reproduces the dependence of H2 bond length on the adsorption distance from MXenes within the framework of Pauling's resonating valence bond theory, revealing the impact of transition metal's ligancy and valence on activating dihydrogen in H2 storage. [ABSTRACT FROM AUTHOR]

Accurate description of electronic excited states of high-spin molecular species is a yet unsolved problem in modern electronic structure theory. A composite computational scheme developed in the present work contributes to solving this task for a challenging case of lanthanide-containing molecules. In the scheme, the highest-spin states whose wavefunctions are dominated by a single Slater determinant are described at the single-reference (SR) CCSD(T) level, whereas the lower-spin states, being inherently multiconfigurational in their nature, are treated with multireference (MR) methods, MRCI and/or CASPT2. An original technique which scales MR results against SR CCSD(T) ones to improve the accuracy in the former is proposed and examined, taking the example of 12 electronic states of gadolinium monoxide, X9Σ−, Y7Σ−, A′9Δ, A1′7Δ, A9Π, A17Π, B9Σ−, B17Σ−, C9Π, C17Π, D9Σ−, and D17Σ−, up to 35 000 cm−1. A multitude of the corresponding Ω (spin-coupled) states was then studied within the state-interacting approach employing the full Breit–Pauli spin–orbit coupling operator with CASSCF-generated ΛS states as a basis. For all ΛS and Ω states, the Gd–O bond lengths, spectroscopic constants ωe, ωexe, αe, and adiabatic excitation energies are obtained. The theoretical predictions are in good agreement with the experimental data, with deviations in excitation energies not exceeding 350 cm−1 (1 kcal/mol). The spectroscopic properties of the yet unobserved electronic states, A′9Δ, A1′7Δ, C9Π, C17Π, D9Σ−, and D17Σ−, are evaluated for the first time. [ABSTRACT FROM AUTHOR]

As conducting polymers become increasingly important in electronic devices, understanding their charge transport is essential for material and device development. Various semi-empirical approaches have been used to describe temporal charge carrier dynamics in these materials, but there have yet to be any theoretical approaches utilizing ab initio molecular dynamics. In this work, we develop a computational technique based on ab initio Car–Parrinello molecular dynamics to trace charge carrier temporal motion in archetypical conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). Particularly, we analyze charge dynamics in a single PEDOT chain and in two coupled chains with different degrees of coupling and study the effect of temperature. In our model we first initiate a positively charged polaron (compensated by a negative counterion) at one end of the chain, and subsequently displace the counterion to the other end of the chain and trace polaron dynamics in the system by monitoring bond length alternation in the PEDOT backbone and charge density distribution. We find that at low temperature (T = 1 K) the polaron distortion gradually disappears from its initial location and reappears near the new position of the counterion. At the room temperature (T = 300 K), we find that the distortions induced by polaron, and atomic vibrations are of the same magnitude, which makes tracking the polaron distortion challenging because it is hidden behind the temperature-induced vibrations. The novel approach developed in this work can be used to study polaron mobility along and between the chains, investigate charge transport in highly doped polymers, and explore other flexible polymers, including n-doped ones. [ABSTRACT FROM AUTHOR]

In situ temperature-dependent crystal structure of lead-free ferroelectric perovskite Ba0.798Ca0.202Zr0.006Ti0.994O3 single crystal was characterized using x-ray diffraction from 170 to 380 K. Three phases were identified at different temperatures of 170, 220, and 298 K, revealing rhombohedral (R3m), orthorhombic (Pmm2), and tetragonal (P4mm) crystal structures, respectively. The change in the bond length and its distortion are reported for both AO12 and BO6 polyhedrons, allowing for the estimation of the spontaneous polarization. The Debye–Waller factor is reported as a function of temperature for A and B-sites. Density-functional theory calculations on the tetragonal phase were performed to obtain information on the distribution of the Ca ions, the local atomic displacements, and the ideal value of the spontaneous polarization of a defect-free crystal at 0 K. We find that Ca prefers to arrange in columnar 2D plates oriented along the tetragonal axis. The Ca ions avoid being next neighbors of Zr; however, the specific arrangement of Ca has only a minor impact on the spontaneous polarization. [ABSTRACT FROM AUTHOR]

Cell adhesion can be significantly influenced by the topography of the substrate surface. However, how the adhesion molecules essentially respond to this topographical stimulus is not fully understood yet. Here, we employ an effective Monte Carlo simulation to systematically investigate a fluctuating membrane interacting with a curved substrate via adhesive proteins. Interestingly, results show that, compared with the flat substrate, curved substrates regulate the membrane adhesion in a bond length dependent manner. The effects of the substrate surface amplitude and wavelength on the number of molecular bonds and adhesion pattern are also extracted from the scaling relationship between the characteristic lateral length of the membrane and the local substrate curvature radius. Furthermore, the local substrate curvature is found to select the bond distribution in terms of the bond length and stiffness. The results suggest that the bond stiffness enhances the clustering of molecular bonds, mainly due to synergistic interactions among these molecular bonds. [ABSTRACT FROM AUTHOR]

We analyze the shear response of grafted polymer chains in shear flow via coarse-grained molecular dynamics simulations with an explicit solvent. We find that the solvent flow penetrates into almost the whole brush for "mushroom"-type brushes but only a few bond distances for dense brushes. In all cases, the external stress on the wall equals the entropic stress associated with the distorted polymer conformations. We find that the external stress increases linearly with shear rate at low rates and sublinearly at high rates. The transition from linear to sublinear scaling occurs where chains react to flow by reorienting. Sublinear scaling with shear rate disappears if the shear rate is nondimensionalized with the effective relaxation time of chain subsegments located in the outer part of the brush that experiences flow. [ABSTRACT FROM AUTHOR]

The structure of zinc aluminosilicate glasses with the composition (ZnO)x(Al2O3)y(SiO2)1−x−y, where 0 ≤ x < 1, 0 ≤ y < 1, and x + y < 1, was investigated over a wide composition range by combining neutron and high-energy x-ray diffraction with 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The results were interpreted using an analytical model for the composition-dependent structure in which the zinc ions do not act as network formers. Four-coordinated aluminum atoms were found to be in the majority for all the investigated glasses, with five-coordinated aluminum atoms as the main minority species. Mean Al–O bond distances of 1.764(5) and 1.855(5) Å were obtained for the four- and five-coordinated aluminum atoms, respectively. The coordination environment of zinc was not observed to be invariant. Instead, it is dependent on whether zinc plays a predominantly network-modifying or charge-compensating role and, therefore, varies systematically with the glass composition. The Zn–O coordination number and bond distance were found to be 4.36(9) and 2.00(1) Å, respectively, for the network-modifying role vs 5.96(10) and 2.08(1) Å, respectively, for the charge-compensating role. The more open coordination environment of the charge-compensator is related to an enhanced probability of zinc finding bridging oxygen atoms as nearest-neighbors, reflecting a change in the connectivity of the glass network comprising four-coordinated silicon and aluminum atoms as the alumina content is increased. [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]

A comprehensive genetic algorithm is used to perform a global search for Cl−(H2O)1–9 and NaCl(H2O)1–9. The structural optimization, energy calculations, vibrational characteristics, and charge distribution were performed at an ab initio high-level theory. Combined with the calculation results of Na+(H2O)1–6 by Wang et al. [Front. Chem. 7, 624 (2019)] in our group, we systematically investigate these three systems at the same theoretical level. A comparison of bond lengths reveals that in Cl−(H2O)n, the inclusion of Na+ to form NaCl(H2O)n reduces the average distance between Cl− and H2O, indicating that Na+ has a stabilizing effect on ionic hydrogen bonds. Conversely, in Na+(H2O)n, the introduction of Cl− weakens the interactions between Na+ and H2O. In the NaCl(H2O)1–9 structures searched by the genetic algorithm, the ground-state configurations correspond to contact ion pairs, and the solvent-separated ion pair structures appear when n = 7. Furthermore, the anharmonic corrected infrared spectra of Cl−(H2O)1–5 and NaCl(H2O)1–4 exhibit good agreement with the experimental results. According to charge analysis of NaCl(H2O)n, it is observed that charge transfer primarily occurs from Cl− to H2O, resulting in the presence of negative charges on the water molecules. These findings are helpful to understand the effects of Na+ and Cl− on hydrated clusters at the molecular level. [ABSTRACT FROM AUTHOR]

The millimeter-wave rotational spectrum of ketene (H2C=C=O) has been collected and analyzed from 130 to 750 GHz, providing highly precise spectroscopic constants from a sextic, S-reduced Hamiltonian in the Ir representation. The chemical synthesis of deuteriated samples allowed spectroscopic measurements of five previously unstudied ketene isotopologues. Combined with previous work, these data provide a new, highly precise, and accurate semi-experimental (reSE) structure for ketene from 32 independent moments of inertia. This reSE structure was determined with the experimental rotational constants of each available isotopologue, together with computed vibration–rotation interaction and electron-mass distribution corrections from coupled-cluster calculations with single, double, and perturbative triple excitations [CCSD(T)/cc-pCVTZ]. The 2σ uncertainties of the reSE parameters are ≤0.0007 Å and 0.014° for the bond distances and angle, respectively. Only S-reduced spectroscopic constants were used in the structure determination due to a breakdown in the A-reduction of the Hamiltonian for the highly prolate ketene species. All four reSE structural parameters agree with the "best theoretical estimate" (BTE) values, which are derived from a high-level computed re structure [CCSD(T)/cc-pCV6Z] with corrections for the use of a finite basis set, the incomplete treatment of electron correlation, relativistic effects, and the diagonal Born–Oppenheimer breakdown. In each case, the computed value of the geometric parameter lies within the statistical experimental uncertainty (2σ) of the corresponding semi-experimental coordinate. The discrepancies between the BTE structure and the reSE structure are 0.0003, 0.0000, and 0.0004 Å for rC–C, rC–H, and rC–O, respectively, and 0.009° for θC–C–H. [ABSTRACT FROM AUTHOR]

We investigate the adiabatic approximation to the exact-exchange kernel for calculating correlation energies within the adiabatic-connection fluctuation–dissipation framework of time-dependent density functional theory. A numerical study is performed on a set of systems having bonds of different character (H2 and N2 molecules, H-chain, H2-dimer, solid-Ar, and the H2O-dimer). We find that the adiabatic kernel can be sufficient in strongly bound covalent systems, yielding similar bond lengths and binding energies. However, for non-covalent systems, the adiabatic kernel introduces significant errors around equilibrium geometry, systematically overestimating the interaction energy. The origin of this behavior is investigated by studying a model dimer composed of one-dimensional, closed-shell atoms, interacting via soft-Coulomb potentials. The kernel is shown to exhibit a strong frequency dependence at small to intermediate atomic separation that affects both the low-energy spectrum and the exchange-correlation hole obtained from the corresponding diagonal of the two-particle density matrix. [ABSTRACT FROM AUTHOR]

A large-scale quantum chemical calculation program, Dcdftbmd, was integrated with a Python-based advanced atomistic simulation program, i-PI. The implementation of a client–server model enabled hierarchical parallelization with respect to replicas and force evaluations. The established framework demonstrated that quantum path integral molecular dynamics simulations can be executed with high efficiency for systems consisting of a few tens of replicas and containing thousands of atoms. The application of the framework to bulk water systems, with and without an excess proton, demonstrated that nuclear quantum effects are significant for intra- and inter-molecular structural properties, including oxygen–hydrogen bond distance and radial distribution function around the hydrated excess proton. [ABSTRACT FROM AUTHOR]

Rare-earth titanate pyrochlores have attracted significant attention for their unique magnetic frustration; however, research on the origin of low-temperature dielectric dispersion and the relationship between dielectric properties and structure lags far behind. Here, by systematically investigating the dielectric properties of representative rare-earth titanates R2Ti2O7 (R = La, Nd, Sm, Er, Yb, and Lu), we demonstrate that R2Ti2O7 with a cubic pyrochlore structure exhibits low-temperature dielectric dispersion behavior, while the other compounds with a monoclinic perovskite-like layered structure possess no dispersion behavior but excellent temperature-stable dielectric property. The dielectric dispersion in cubic pyrochlores arises from the structural distortion. Furthermore, the existence of structural distortion is affirmed by the anomalous phonon softening of A1g Raman mode around the dielectric dispersion temperature, and the origin of the structural distortion is attributed to anharmonic phonon–phonon interactions induced by intrinsic vacant oxygen at Wyckoff 8a sites. In addition, with increasing ionic radius from R = Lu to Sm, the increased lattice parameter leads to varied bond length and bond angle of Ti-O(1)-Ti, which strengthens the local lattice distortion of TiO(1)6 octahedra and thus enhances diffusion degree of dielectric dispersion. On the other hand, the absence of intrinsic vacant oxygen site hardly gives rise to the local structural distortion and thus no dielectric dispersion in monoclinic R2Ti2O7. Our work not only clarifies the mechanism of dielectric dispersion but also gives a comprehensive perspective on the structure–property relationship of rare-earth titanates R2Ti2O7, and thus lays a solid foundation for further work on related materials. [ABSTRACT FROM AUTHOR]

Redox gating involves the use of reversible redox functionalities combined with ionic electrolytes to substantially alter the charge carrier density in functional condensed materials. This modification leads to the emergence of physical properties not observed in the original material. In our study, we focus on redox gating applied to a LaNiO3 (001) film within a field-effect device and identify a critical gate voltage of 0.7 V. Hall measurements indicate that redox gating markedly increases the charge carrier density in LaNiO3, reaching over 1014 cm−2. This increase is primarily due to the injection of electrons into LaNiO3, which offsets the existing hole carriers. These adjustments in the carrier concentration result in reversible lattice expansion in LaNiO3 when gate voltages are below 0.7 V. This expansion correlates well with theoretical models that consider adjustments to the Ni–O bond length, influenced by oxygen ligand holes. Conversely, at gate voltages above 0.7 V, there are significant changes in resistivity, lattice structure, and Ni valence, stemming from the formation of oxygen vacancies in the LaNiO3 film. [ABSTRACT FROM AUTHOR]

The multiferroic properties of TbMnO3 demonstrate high versatility under applied pressure, making the material potentially suitable for use in flexible electronics. Here, we report on the preparation of elastic freestanding TbMnO3 membranes with dominant (001) or (010) crystallographic out-of-plane orientation. Membranes with a thickness of 20 nm display orthorhombic bulk-like relaxed lattice parameters with strong suppression of twinning for the (010) oriented membranes. Strain in flexible membranes was tuned using a commercial strain cell device and characterized by Raman spectroscopy. The B1g out-of-phase oxygen-stretching mode, representative of the Mn–O bond distance, systematically shifts to lower energy with increasing strain (εmax ≈ 0.5%). The flexibility and elastic properties of the membranes allow for specific manipulation of the multiferroic state by strain, whereas the choice of the crystallographic orientation gives the possibility of an in- or out-of-plane electric polarization. [ABSTRACT FROM AUTHOR]

The multiferroic properties of TbMnO3 demonstrate high versatility under applied pressure, making the material potentially suitable for use in flexible electronics. Here, we report on the preparation of elastic freestanding TbMnO3 membranes with dominant (001) or (010) crystallographic out-of-plane orientation. Membranes with a thickness of 20 nm display orthorhombic bulk-like relaxed lattice parameters with strong suppression of twinning for the (010) oriented membranes. Strain in flexible membranes was tuned using a commercial strain cell device and characterized by Raman spectroscopy. The B1g out-of-phase oxygen-stretching mode, representative of the Mn–O bond distance, systematically shifts to lower energy with increasing strain (εmax ≈ 0.5%). The flexibility and elastic properties of the membranes allow for specific manipulation of the multiferroic state by strain, whereas the choice of the crystallographic orientation gives the possibility of an in- or out-of-plane electric polarization. [ABSTRACT FROM AUTHOR]

Minimum energy path (MEP) search is a vital but often very time-consuming method to predict the transition states of versatile dynamic processes in chemistry, physics, and materials science. In this study, we reveal that the largely displaced atoms in the MEP structures maintain transient chemical bond lengths resembling those of the same type in the stable initial and final states. Based on this discovery, we propose an adaptive semirigid body approximation (ASBA) to construct a physically reasonable initial guess for the MEP structures, which can be further optimized by the nudged elastic band method. Examination of several distinct dynamical processes in bulk, on crystal surface, and through two-dimensional system shows that our transition state calculations based on the ASBA results are robust and significantly faster than those based on the popular linear interpolation and image-dependent pair potential methods. [ABSTRACT FROM AUTHOR]