Ab Initio Potential Research Articles

Radiometric forces exerted on a perforated membrane

The radiometric force exerted on a thin perforated membrane and the heat flux from the membrane to a surrounding gas are calculated by the direct simulation Monte Carlo method over wide ranges of the gas rarefaction and membrane porosity. Ab initio potentials are used to model the intermolecular collisions. We find that perforations increase the force several times in the viscous regime of flow but decrease the force in the free-molecular and transitional regimes. The influence of the accommodation coefficients is studied by applying the Cercignani–Lampis model. The effects of gas species, degree of non-equilibrium, and environment temperature are found to have relatively small effects on dimensionless quantities such that the reported results can be applied to wide ranges of these factors and, hence, to numerous practical situations such as the levitation of centimeter-scale membranes at upper atmospheric altitudes.

Collision rate coefficients for C7N− and C10H− with H2

ABSTRACT The anions C$_7$N$^-$ and C$_{10}$H$^-$ are the two longest of the linear (C,N)-bearing and (C,H)-bearing chains that have so far been detected in the interstellar medium (ISM). In order to glean information on their collision-induced rotational state-changing processes, we analyse the general features of new ab initio potentials describing the interaction of both linear anions with H$_2$, one of the most abundant partners in their ISM environment. We employ an artificial neural network fit of the reduced-dimensionality potential energy surface for C$_7$N$^-$...H$_2$ interaction and discuss in detail the spatial features in terms of multipolar radial coefficients. For the C$_{10}$H$^-$...H$_2$ interaction, we use the initial grid of two-dimensional raw points to generate by quadrature the Legendre expansion directly, further including the long-range terms as discussed in the main text. Quantum scattering calculations are employed to obtain rotationally inelastic cross-sections, for collision energies in the range of 10$^{-4}$ to 400 cm$^{-1}$. From them we generate the corresponding inelastic rate coefficients as a function of temperature covering the range from 10 to 50 K. The results for the rate coefficients for the longest cyanopolyyne are compared with the earlier results obtained for the smaller terms of the same series, also in collision with H$_2$. We obtain that the inelastic rate coefficients for the long linear anions are all fairly large compared with the earlier systems. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are illustrated in our conclusions.

Resource Optimization for Quantum Dynamics with Tensor Networks: Quantum and Classical Algorithms.

The exponential scaling of the quantum degrees of freedom with the size of the system is one of the biggest challenges in computational chemistry and particularly in quantum dynamics. We present a tensor network approach for the time-evolution of the nuclear degrees of freedom of multiconfigurational chemical systems at a reduced storage and computational complexity. We also present quantum algorithms for the resultant dynamics. To preserve the compression advantage achieved via tensor network decompositions, we present an adaptive algorithm for the regularization of nonphysical bond dimensions, preventing the potentially exponential growth of these with time. While applicable to any quantum dynamical problem, our method is particularly valuable for dynamical simulations of nuclear chemical systems. Our algorithm is demonstrated using ab initio potentials obtained for a symmetric hydrogen-bonded system, namely, the protonated 2,2'-bipyridine, and compared to exact diagonalization numerical results.

Ab Initio Potentials for the Ground S0 and the First Electronically Excited Singlet S1 States of Benzene-Helium with Application to Tunneling Intermolecular Vibrational States.

We present new ab initio intermolecular potential energy surfaces for the benzene-helium complex in its ground (S0) and first excited (S1) states. The coupled-cluster level of theory with single, double, and perturbative triple excitations, CCSD(T), was used to calculate the ground state potential. The excited state potential was obtained by adding the excitation energies S0 → S1 of the complex, calculated using the equation of motion approach EOM-CCSD, to the ground state potential interaction energies. Analytical potentials are constructed and applied to study the structural and vibrational dynamics of benzene-helium. The binding energies and equilibrium distances of the ground and excited states were found to be 89 cm-1, 3.14 Å and 77 cm-1, 3.20 Å, respectively. The calculated vibrational energy levels exhibit tunneling of He through the benzene plane and are in reasonable agreement with recently reported experimental values for both the ground and excited states [Hayashi, M.; Ohshima, Y. J. Phys. Chem. Lett. 2020, 11, 9745]. Prospects for the theoretical study of complexes with large aromatic molecules and He are also discussed.

Encoding a Many-Body Potential Energy Surface into a Grid-Based Matrix Product Operator.

An efficient algorithm for compressing a given many-body potential energy surface (PES) of molecular systems into a grid-based matrix product operator (MPO) is proposed. The PES is once represented by a full-dimensional or truncated many-body expansion form, which is obtained by ab initio calculations at each grid mesh point, and then all terms in the expansion are compressed and merged into a single MPO while maintaining the bond dimension of the MPO as small as possible. It was shown that the ab initio PES of the H2CO was compressed by more than 2 orders of magnitude in the size of the site operators without loss of accuracy. By the use of grid basis, the tensor rank of the site operators of the MPO is reduced from four to three due to the diagonal nature of the position-dependent operators on grid basis, which significantly reduces the computational cost of the tensor contractions required in the real and imaginary time evolution of the matrix product state (MPS) wave functions with the grid-based MPO (Grid-MPO) Hamiltonian. Similar to other grid-based methods, Grid-MPO is easily applicable to any kinds of potentials of molecular systems, such as analytical empirical model potentials expressed by position operators and ab initio potentials, if the values at the grid points are available. Using the Grid-MPO combined with the MPS, we calculated the time correlation function of the Eigen cation to predict the infrared spectrum and compared with the experimental and the previous theoretical studies. The actual scaling with the size of systems was examined for the multidimensional Henon-Heiles Hamiltonian. It was shown that the method is considerably accelerated by the graphic processing unit (GPU) because the sizes of site operators were kept small and all tensors were able to be stored on the VRAM of a GPU.

Asymetrical shape of C–He lines in the ultraviolet

ABSTRACT We present the first theoretical line profile calculations of the ultraviolet spectral lines of carbon perturbed by helium using a semiclassical collision approach and high-quality ab initio potentials and electronic transition dipole moments. The temperature range is from 5000 to 8000 K. These results are important for astrophysical modelling of spectra in atmospheres of white dwarf stars showing atomic carbon in an helium atmosphere. Beyond the conventional symmetrical Lorentzian core at low He density, these lines exhibit a blue asymmetric behaviour. This blue asymmetry is a consequence of low maxima in the corresponding C–He potential energy difference curves at short internuclear distances. The collisional profiles are carefully examined and their perturber density dependence allow to understand the various line shapes of the observed carbon spectral lines in helium-rich white dwarf photosphere where the He perturber densities reach several 1021 cm−3.

Understanding cellulose pyrolysis via ab initio deep learning potential field

Comprehensive and dynamic studies of cellulose pyrolysis reaction mechanisms are crucial in designing experiments and processes with enhanced safety, efficiency, and sustainability. The details of the pyrolysis mechanism are not readily available from experiments but can be better described via molecular dynamics (MD) simulations. However, the large size of cellulose molecules challenges accurate ab initio MD simulations, while existing reactive force field parameters lack precision. In this work, precise ab initio deep learning potentials field (DPLF) are developed and applied in MD simulations to facilitate the study of cellulose pyrolysis mechanisms. The formation mechanism and production rate of both valuable and greenhouse products from cellulose at temperatures larger than 1073 K are comprehensively described. This study underscores the critical role of advanced simulation techniques, particularly DLPF, in achieving efficient and accurate understanding of cellulose pyrolysis mechanisms, thus promoting wider industrial applications.

New theoretical study of potassium perturbed by He and a comparison to laboratory spectra

The visible and near-infrared spectra of late L- and T-type dwarf stars are dominated in large part by the resonance lines of neutral Na and K. It is the collision broadening of these atomic lines by H2 and He in the stellar atmosphere that determines the continuum from below 0.5 µm to above 0.9 µm in the spectrum. Their line profiles can be detected as far as 3000 cm−1 from the line center in T dwarfs and consequently an accurate and detailed determination of the complete profile, including the extreme far wing, is required to model the contribution of these strong alkali resonance lines to brown dwarf spectra. We report on our new calculations of unified line profiles of K perturbed by He using ab initio potential data for the conditions prevailing in cool substellar brown dwarfs and hot dense planetary atmospheres with temperatures from Teff = 500 to 3000 K. For such objects with atmospheres of H2 and He, conventional laboratory absorption spectroscopy can be used to examine the line wings and test the line shape theories and molecular potentials. We find that an analytical Lorentzian profile is useful for a few cm−1 from the line center, but not in the line wings, where the radiative transfer is a consequence of the K–He radiative collisions that are sensitive to the interaction potentials. Tables of the K–He absorption coefficients of the resonance lines allow accurate model atmospheres and synthetic spectra. For this purpose, we present new opacities from comprehensive line shape theory incorporating accurate ab initio potentials. Use of these new tables for the modeling of emergent spectra will be an improvement over previous line shape approximations based on incomplete or inaccurate potentials. We also present Lorentzian impact parameters obtained in the semi-classical and quantum theory for the K 4s − 4p resonance line centered at 0.77 µm specifically for the line core regime.

Vapor-liquid equilibrium and thermodynamic properties of saturated argon and krypton from Monte Carlo simulations using abinitio potentials.

Vapor-liquid equilibria and thermodynamic properties of saturated argon and krypton were calculated by semi-classical Monte Carlo simulations with the NpT + test particle method using abinitio potentials for the two-body and nonadditive three-body interactions. The NpT + test particle method was extended to the calculation of second-order thermodynamic properties, such as the isochoric and isobaric heat capacities or the speed of sound, of the saturated liquid and vapor by using our recently developed approach for the systematic calculation of arbitrary thermodynamic properties in the isothermal-isobaric ensemble. Generally, the results for all simulated properties agree well with experimental data and the current reference equations of state for argon and krypton. In particular, the results for the vapor pressure and for the density and speed of sound of the saturated liquid and vapor agree with the most accurate experimental data for both noble gases almost within the uncertainty of these data, a level of agreement unprecedented for many-particle simulations. This study demonstrates that the vapor-liquid equilibrium and thermodynamic properties at saturation of a pure fluid can be predicted by Monte Carlo simulations with high accuracy when the intermolecular interactions are described by state-of-the-art abinitio pair and nonadditive three-body potentials and quantum effects are accounted for.

Characterization of iron(III) in aqueous and alkaline environments with abinitio and ReaxFF potentials.

The iron(III) complexes [Fe(H2O)n(OH)m]3-m (n + m = 5, 6, m ≤ 3) and corresponding proton transfer reactions are studied with total energy calculations, the nudged elastic band (NEB) method, and molecular dynamics (MD) simulations using abinitio and a modification of reactive force field potentials, the ReaxFF-AQ potentials, based on the implementation according to Böhm et al. [J. Phys. Chem. C 120, 10849-10856 (2016)]. Applying abinitio potentials, the energies for the reactions [Fe(H2O)n(OH)m]3-m + H2O → [Fe(H2O)n-1(OH)m+1]2-m + H3O+ in a gaseous environment are in good agreement with comparable theoretical results. In an aqueous (aq) or alkaline environment, with the aid of NEB computations, respective minimum energy paths with energy barriers of up to 14.6 kcal/mol and a collective transfer of protons are modeled. Within MD simulations at room temperature, a permanent transfer of protons around the iron(III) ion is observed. The information gained concerning the geometrical and energetic properties of water and the [Fe(H2O)n(OH)m]3-m complexes from the abinitio computations has been used as reference data to optimize parameters for the O-H-Fe interaction within the ReaxFF-AQ approach. For the optimized ReaxFF-AQ parameter set, the statistical properties of the basic water model, such as the radial distribution functions and the proton hopping functions, are evaluated. For the [Fe(H2O)n(OH)m]3-m complexes, it was found that while geometrical and energetic properties are in good agreement with the abinitio data for gaseous environment, the statistical properties as obtained from the MD simulations are only partly in accordance with the abinitio results for the iron(III) complexes in aqueous or alkaline environments.

Accurate thermodynamic properties of the neon fluid from ab initio potentials and uncertainty assessments of simulation data

Molecular dynamics simulations are employed to investigate the internal energy, pρT properties, isochoric heat capacity, and sound speed of the neon fluid. Reliable two- and three-body ab initio potentials are used to obtain data covering a wide temperature and density range of (25 to 725) K and (0.05 to 70) mol⋅L−1 in the gas, liquid, and supercritical phases. The uncertainty of simulation data are evaluated based on the uncertainty of the two-body potential and that of the simulation method. The so-called quantum Feynman-Hibbs modification is introduced to account for the quantum effects at low temperatures. The two-body ab initio potential is combined with the three-body ab initio potential to evaluate the influence of multi-body interactions at high densities. The corresponding results are almost the same as those by the two-body ab initio potential, so the three-body contributions are neglected to accelerate computational speed. In general, the thermodynamic property data of this work show agreement with the experimental data in the literature as well as the NIST data at temperatures above 120 K and densities below 45 mol⋅L−1.

PES and transport properties of the He⋯HBr complex from kinetic theory and molecular dynamics simulations.

The ab initio intermolecular potential of the He⋯HBr van der Waals (vdW) complex was calculated at the CCSD(T)/a5zBF level of theory and expanded in terms of the orthogonal Legendre polynomials. The PES then was implemented to calculate the interaction viscosity (η12) and diffusion (D12) coefficients through classical Mason-Monchick approximation (MMA), quantum mechanical close-coupling (CC), and molecular dynamics (MD) simulations. Energy-dependent Senftleben-Beenakker (SB) cross-sections were calculated using rotationally averaged cross-sections, and Boltzmann averaging was used to reveal the temperature dependence of the SB cross-sections over the temperature range of T = 50-1000 K. The calculated transport properties from MMA are in close agreement with the CC results, especially for temperatures lower than T = 900 K. The ab initio potential data then were used to derive LJ (12,6) and Vashishta MD force fields, and the equilibrium MD simulation methods were implemented to extract η12 and D12 coefficients using Einstein formulas. It was found that the Vashishta 3-body interaction potential model shows better accuracy than the LJ (12,6) model in MD simulations of D12. For η12, however, both MD potential models are successful, and an average absolute deviation of lower than 1% was obtained when compared to the quantum mechanical CC method.

New studies and predictions for nuclear clustering and dynamics in the ab initio symmetry-adapted framework

We discuss recent studies and predictions for nuclear clustering and dynamics within the framework of the ab initio symmetry-adapted no-core shell model, which has opened new domains of the nuclear chart. In this framework, we show the emergence from first principles of collectivity and clustering in light to mediummass nuclei, with implications for constructing ab initio optical potentials, for studying clustering in stable and unstable nuclei, for reproducing enhanced deformations without effective charges, and for the formation of clusters and its sensitivity to the underlying inter-nucleon force.

Quantum study of the rovibrational relaxation of HF by collision with 4He on a new potential energy surface.

The HF molecule is considered the main reservoir of fluorine in the interstellar medium (ISM). Also, the interactions of this molecule with the most common atoms and molecules in the ISM have attracted great interest from the astrochemical community. Collisions between HF and helium have recently caused controversy following a study using a two-dimensional SAPT potential energy surface (PES) that exhibited large discrepancies with previous scattering calculations based on more recent ab initio potentials. To address this issue, our current work aims to develop the most precise three-dimensional PES for the HF+He system. We employ the size-consistent CCSD(T) method in conjunction with the aug-cc-pV6Z basis set. The main features of the new PES as well as the bound states of the He-HF complex are compared to the existing data. The new PES is then utilised to conduct close coupling calculations that demonstrate He-HF as a good instance of vibration-rotation near resonant energy transfer. The novel rate coefficients will be accessible via the BASECOL database, and the use of the new PES is advised when describing HF in helium droplets.

Photophysics of a nucleic acid-protein crosslinking model strongly depends on solvation dynamics: an experimental and theoretical study.

We present a combined experimental and theoretical study of the photophysics of 5-benzyluracil (5BU) in methanol, which is a model system for interactions between nucleic acids and proteins. A molecular dynamics study of 5BU in solution through efficient DFT-based hybrid ab initio potentials revealed a remarkable conformational flexibility - allowing the population of two main conformers - as well as specific solute-solvent interactions, which both appear as relevant factors for the observed 5BU optical absorption properties. The simulated absorption spectrum, calculated on such an ensemble, enabled a molecular interpretation of the experimental UV-Vis lowest energy band, which is also involved in the induced photo-reactivity upon irradiation. In particular, the first two excited states (mainly involving the uracil moiety) both contribute to the 5BU lowest energy absorption. Moreover, as a key finding, the nature and brightness of such electronic transitions are strongly influenced by 5BU conformation and the microsolvation of its heteroatoms.

Improved Quantum-Classical Treatment of N2-N2 Inelastic Collisions: Effect of the Potentials and Complete Rate Coefficient Data Sets.

In this study, complete (i.e., including all vibrational quantum numbers in an N2 vibrational ladder) data sets of vibration-to-vibration and vibration-to-translation rate coefficients for N2-N2 collisions are explicitly computed along with transport properties (shear and bulk viscosity, thermal conductivity, and self-diffusion) in the temperature range 100-9000 K. To reach this goal, we improved a mixed quantum-classical (MQC) dynamics approach by lifting the constraint of a Morse treatment of the vibrational wave function and intramolecular potential and permitting the use of more realistic and flexible representations. The new formulation has also allowed us to separately analyze the role of intra- and intermolecular potentials on the calculated rates and properties. Ab initio intramolecular potentials are indispensable for highly excited vibrational states, though the Morse potential still gives reasonable values up to v = 20. An accurate description of the long-range interaction and the van der Waals well is a requisite for the correct reproduction of qualitative and quantitative rate coefficients, particularly at low temperatures, making physically meaningful analytical representations still the best choice compared to currently available ab initio potential energy surfaces. These settings were used to directly compute the MQC rates corresponding to a large number of initial vibrational quantum numbers, and the missing intermediate values were predicted using a machine learning technique (i.e., the Gaussian process regression approach). The obtained values are reliable in the wide temperature range employed and are therefore valuable data for many communities dealing with nonlocal thermal equilibrium conditions in different environments.

Ab initio modelling of transport phenomena in multi-component mixtures of rarefied gases

The direct simulation Monte Carlo method based on ab initio potentials is applied to model transport phenomena in binary, ternary and quaternary mixtures of noble gases. To this end, the Couette and Fourier problems are solved over the whole range of the rarefaction parameter spanning the near free-molecular, transitional, and slip flow regimes. Moreover, analytical solutions are obtained in the limits of the free-molecular and continuous medium regimes of flow. As a result, the shear stress, heat flux through multi-component mixtures, distributions of velocity, temperature, and mole fractions of each species are calculated as a function of the gas rarefaction. An analysis of these data points out the properties which are strongly affected by the chemical composition. It is found that the largest deviations of characteristics of mixtures from those of a single gas are observed for the binary mixture of helium and krypton, while their deviations for the ternary and quaternary mixtures are smaller. A temperature variation in a mixture leads to non-uniform distributions of chemical composition due to the thermal diffusion phenomenon. Such redistributions are analyzed in both problems and their effect on the heat and momentum transfer is evaluated. The reported results can be used to evaluate the main factors determining transport phenomena in practical applications such as vacuum systems, microfluidics, gas separation technology, space research etc.

Simulations of the thermodynamic properties of the helium fluid from the state-of-the-art ab initio potentials and their uncertainty estimation

ABSTRACT The molecular dynamics simulation method is used to study the internal energy, pressure, isochoric heat capacity, and sound speed of helium based on the state-of-the-art ab initio potentials. The simulations cover a wide temperature and density range of (20–2000) K and (0.0005–70) m o l L − 1 . The uncertainty of simulation data are evaluated based on the uncertainty of the potential and the uncertainty of the simulation method. At temperatures below 300 K, the quantum Feynman-Hibbs modified potential and the Wigner-Kirkwood modified potential are introduced and the results are almost the same as those by the original ab initio potential. The modified potentials can not reasonably describe the quantum effects for the helium fluid at low temperatures, which become obvious below 200 K. The two-body ab initio potential is combined with the three-body ab initio potential to evaluate the influence of multi-body interactions at high densities. When the density is lower than 45 m o l L − 1 , the contribution of the three-body term to our simulation data is not significant. As a result, the three-body potential is omitted in our calculations to improve the overall computational efficiency. The thermodynamic property data of this work show agreement with the experimental data in the literature as well as the NIST Refprop 10.0 data at temperatures above 200 K and densities below 45 m o l L − 1 .

Molecular Oxygen Trimer: Multiplet Structures and Stability.

We present a detailed theoretical study of the molecular oxygen trimer where the potential energy surfaces of the seven multiplet states have been calculated by means of a pair approximation with very accurate dimer ab initio potentials. In order to obtain all the states a matrix representation of the potential using the uncoupled spin representation has been applied. The and states are nearly degenerate and low-lying isomers appear for most multiplicities. A crucial point in deciding the relative stabilities is the zero-point energy which represents a sizable fraction of the electronic well-depth. Therefore, we have performed accurate diffusion Monte Carlo studies of the lowest state in each multiplicity. Analysis of the wavefunction allows a deeper interpretation of the cluster structures, finding that they are significantly floppy in most cases.

Viscous and thermal velocity slip coefficients via the linearized Boltzmann equation with ab initio potential

The viscous and thermal velocity slip coefficients of various monatomic gases are computed via the linearized classical Boltzmann equation, with ab initio potential, subject to Maxwell and Cercignani–Lampis boundary conditions. Both classical and quantum interatomic interactions are considered. Comparisons with hard sphere and Lennard–Jones potentials, as well as the linearized Shakhov model are performed. The produced database is dense, covers the whole range of the accommodation coefficients and is of high accuracy. Using symbolic regression, very accurate closed form expressions of the slip coefficients, easily implemented in the future computational and experimental works, are deduced. The thermal slip coefficient depends, much more than the viscous one, on the intermolecular potential. For example, in the case of diffuse scattering, the relative differences in the viscous slip coefficient data between HS and AI potentials are less than 4%, whilst the corresponding ones in the thermal slip coefficient data are about 6% for He, reaching 15% for Xe. Quantum effects are considered for He, at temperatures 1–104 K to deduce that deviations from the classical behaviour are not important in the viscous slip coefficient, but they become important in the thermal slip coefficient, where the differences between the classical and quantum approaches reach 15% at 1 K. The computational effort of solving the linearized Boltzmann equation with ab initio and Lennard–Jones potentials is the same. Since ab initio potentials do not contain any adjustable parameters, it is recommended to use them at any temperature.