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At least 361 records · Page 20

Bond order predictions using deep neural networks

Machine learning is an extremely powerful tool for the modern theoretical chemist since it provides a method for bypassing costly algorithms for solving the Schrödinger equation. Already, it has proven able to infer molecular and atomic properties such as charges, enthalpies, dipoles, excited state energies, and others. Most of these machine learning algorithms proceed by inferring properties of individual atoms, even breaking down total molecular energy into individual atomic contributions. In this paper, we introduce a modified version of the Hierarchically Interacting Particle Neural Network (HIP-NN) capable of making predictions on the bonds between atoms rather than on the atoms themselves. We train the modified HIP-NN to infer bond orders for a large number of small organic molecules as computed via the Natural Bond Orbital package. We demonstrate that the trained model is extensible to molecules much larger than those in the training set by studying its performance on the COMP6 dataset. This method has applications in cheminformatics and force field parameterization and opens a promising future for machine learning models to predict other quantities that are defined between atoms such as density matrix elements, Hamiltonian parameters, and molecular reactivities.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A simple theoretical model for calculating and parameterizing the ionospheric photoelectron flux

A method for calculating the ionospheric photoelectron flux is developed which uses the concept of average electron energy loss to simplify the calculation of the degraded electron spectrum. This method requires only a knowledge of the total inelastic electron impact cross sections and can be used for the calculation of all secondary ion and excited state production rates. The simple calculation reduces the computing time by a factor of 10 and considerably reduces storage requirements. It is found that the ionospheric photoelectron flux in the local equilibrium region is directly proportional to the attenuated solar EUV flux, which is a function only of the total neutral column density, and is independent of the neutral density composition. Thus, it is shown that electron impact cross section can be chosen so that this method may also be used to parameterize the measured ionospheric photoelectron fluxes.

Richards, P. G.↗

Laser induced photoluminescence spectroscopy of cometary radicals

Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

Jackson, W. M.↗

Optical properties of a diamond NV color center from capped embedded multiconfigurational correlated wavefunction theory

Diamond defects are among the most promising qubits. Modeling their properties through accurate quantum mechanical simulations can further their development into robust units of information. We use the recently developed capped density functional embedding theory (capped-DFET) with the multiconfigurational n-electron valence second-order perturbation theory to characterize the electronic excitation energies for different spin manifolds of the well-characterized negatively charged substitutional N defect adjacent to a vacancy (V C ) in diamond (N C V C − ). We successfully reproduce vertical excitation energies for both triplet and singlet states of N C V C − with errors < 0.1 eV. Unlike other embedding methods, capped-DFET exhibits robust predictions that are approximately independent of the embedded cluster size: it only requires a cluster to contain the defect atoms and their nearest neighbors (as small as a 40-atom capped cluster). Furthermore, our method is free from slowly converging Coulomb interactions between charged defects, and thus also only weakly dependent on supercell size.

Chemistry↗

Thermonuclear 28 P(p, γ ) 29 S reaction rate and astrophysical implication in ONe nova explosion

An accurate 28 P(p, γ) 29 S reaction rate is crucial to defining the nucleosynthesis products of explosive hydrogen burning in ONe novae. Using the recently released nuclear mass of 29 S, together with a shell model and a direct capture calculation, we reanalyzed the 28 P(p, γ) 29 S thermonuclear reaction rate and its astrophysical implication. We focus on improving the astrophysical rate for 28 P(p, γ) 29 S based on the newest nuclear mass data. Our goal is to explore the impact of the new rate and associated uncertainties on the nova nucleosynthesis. We evaluated this reaction rate via the sum of the isolated resonance contribution instead of the previously used Hauser-Feshbach statistical model. The corresponding rate uncertainty at different energies was derived using a Monte Carlo method. Nova nucleosynthesis is computed with the 1D hydrodynamic code SHIVA. The contribution from the capture on the first excited state at 105.64 keV in 28 P is taken into account for the first time. We find that the capture rate on the first excited state in 28 P is up to more than 12 times larger than the ground-state capture rate in the temperature region of 2.5 × 10 7 K to 4 × 10 8 K, resulting in the total 28 P(p, γ) 29 S reaction rate being enhanced by a factor of up to 1.4 at ~1 × 10 9 K. In addition, the rate uncertainty has been quantified for the first time. It is found that the new rate is smaller than the previous statistical model rates, but it still agrees with them within uncertainties for nova temperatures. The statistical model appears to be roughly valid for the rate estimation of this reaction in the nova nucleosynthesis scenario. Using the 1D hydrodynamic code SHIVA, we performed the nucleosynthesis calculations in a nova explosion to investigate the impact of the new rates of 28 P(p, γ) 29 S. Our calculations show that the nova abundance pattern is only marginally affected if we use our new rates with respect to the same simulations but statistical model rates. Finally, the isotopes whose abundance is most influenced by the present 28 P(p, γ) 29 S uncertainty are 28 Si, 33,34 S, 35,37 Cl, and 36 Ar, with relative abundance changes at the level of only 3% to 4%.

Astronomy & Astrophysics↗

Experimental modal analysis

Experimental modal analysis is extremely important with regard to verification of analytical models, identification of vibration and acoustic problems, and structural modification and sensitivity analysis. With the expanding access of the testing environment to computational power, the complexity of existing approaches, as well as the development of new approaches, to the estimation of modal parameters has grown tremendously. Currently, the state of the art in experimental modal analysis involves methods that can be grouped in four categories: forced normal mode excitation method, frequency response function method, damped complex exponential function method, and mathematical input-output model methods. The theoretical basis of each of these general approaches, with appropriate references, is reviewed briefly.

Allemang, R. J.↗

Theoretical study of the scandium and yttrium halides

The X1Sigma(+) ground states and a3Delta excited states of the diatomic halides of Sc and Y are characterized theoretically, using the SDCI coupled-pair functional method and the state-averaged CASSCF method to determine the spectroscopic constants and related properties. The techniques employed are discussed, and the results are presented in extensive tables. The dissociation energies are given as D0 = 6.00 eV for ScF, 4.55 eV for ScCl, 3.90 eV for ScBr, 6.72 eV for YF, 5.36 eV for YCl, and 4.74 eV for YBr.

Langhoff, Stephen R.↗

Quantum computation of mass gap in an asymptotically free theory

In relativistic field theories, the mass spectrum is given by the difference between the energy of the vacuum and the excited states. Near the continuum limit, the cancellation between these two values leads to loss of precision. We propose a method to extract the mass gap directly using quantum computers and apply it to a particular version of the nonlinear $σ$-model with the correct continuum limit and perform calculations in quantum hardware (at strong coupling) and simulation in classical computers (at weak coupling).

Bedaque, Paulo F. [Maryland U.] (ORCID:00000001521↗

Two-photon excitation cross section in light and intermediate atoms in frozen-core LS-coupling approximation

Using the method of explicit summation over the intermediate states two-photon absorption cross sections in light and intermediate atoms based on the simplistic frozen-core approximation and LS coupling have been formulated. Formulas for the cross section in terms of integrals over radial wave functions are given. Two selection rules, one exact and one approximate, valid within the stated approximations are derived. The formulas are applied to two-photon absorptions in nitrogen, oxygen, and chlorine. In evaluating the radial integrals, for low-lying levels, the Hartree-Fock wave functions, and for high-lying levels, hydrogenic wave functions obtained by the quantum-defect method have been used. A relationship between the cross section and the oscillator strengths is derived.

Omidvar, K.↗

The equation of state for stellar envelopes. II - Algorithm and selected results

A free-energy-minimization method for computing the dissociation and ionization equilibrium of a multicomponent gas is discussed. The adopted free energy includes terms representing the translational free energy of atoms, ions, and molecules; the internal free energy of particles with excited states; the free energy of a partially degenerate electron gas; and the configurational free energy from shielded Coulomb interactions among charged particles. Internal partition functions are truncated using an occupation probability formalism that accounts for perturbations of bound states by both neutral and charged perturbers. The entire theory is analytical and differentiable to all orders, so it is possible to write explicit analytical formulas for all derivatives required in a Newton-Raphson iteration; these are presented to facilitate future work. Some representative results for both Saha and free-energy-minimization equilibria are presented for a hydrogen-helium plasma with N(He)/N(H) = 0.10. These illustrate nicely the phenomena of pressure dissociation and ionization, and also demonstrate vividly the importance of choosing a reliable cutoff procedure for internal partition functions.

Mihalas, Dimitri↗

Strongly Correlated States of Transition Metal Spin Defects: The Case of an Iron Impurity in Aluminum Nitride

We investigate the electronic properties of an exemplar transition metal impurity in an insulator, with the goal of accurately describing strongly correlated defect states. Here, we consider iron in aluminum nitride, a material of interest for hybrid quantum technologies, and we carry out calculations with quantum embedding methods, density matrix embedding theory (DMET) and quantum defect embedding theory (QDET), and with spin-flip time-dependent density functional theory (TDDFT). We show that both DMET and QDET accurately describe the ground state and low-lying excited states of the defect and that TDDFT yields photoluminescence spectra in agreement with experiments. In addition, we provide a detailed discussion of the convergence of our results as a function of the active space used in the embedding methods, thus defining a protocol to obtain converged data directly comparable with experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion Monte Carlo approaches for studying nuclear quantum effects in fluxional molecules

Abstract Diffusion quantum Monte Carlo (DMC) provides a powerful approach for obtaining the ground state energy and wave function of molecules, ions, and molecular clusters. The approach is uniquely well suited for studies of fluxional molecules, which undergo large amplitude vibrational motions even in their ground state. In contrast to the electronic structure problem, where the wave function must be antisymmetric with respect to exchange of any pair of electrons, the wave function for the ground vibrational state is nodeless. This greatly simplifies the application of DMC for vibrational problems. Because there is not a single potential function that can be used to describe the intramolecular and intermolecular interactions in all molecular systems, most methods that are used to describe nuclear quantum effects rely on a carefully chosen zero‐order description of the molecular vibrations. In contrast, DMC calculations can be performed in Cartesian coordinates, making the DMC algorithm easily transferable between different chemical systems. In this contribution, the theory that underlies DMC will be discussed along with important considerations for performing DMC calculations. Extensions for evaluating vibrationally excited states and molecular properties are also discussed. Insights that can be obtained from DMC calculations are illustrated in the context of the protonated water clusters. This article is categorized under: Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods Theoretical and Physical Chemistry > Spectroscopy

Chemistry↗

N -representability violations in truncated equation-of-motion coupled-cluster methods

One-electron reduced density matrices (1RDMs) from equation-of-motion (EOM) coupled-cluster with single and double excitations (CCSD) calculations are analyzed to assess their N-representability (i.e., whether they are derivable from a physical N-electron state). We identify EOM-CCSD stationary states whose 1RDMs violate either ensemble-state N-representability conditions or pure-state conditions known as generalized Pauli constraints. As such, these 1RDMs do not correspond to any physical N-electron state. Unphysical states are also encountered in the course of time-dependent EOM-CC simulations; when an external field drives transitions between a pair of stationary states with pure-state N-representable 1RDMs, the 1RDM of the time-dependent state can violate ensemble-state conditions. Furthermore, these observations point to potential challenges in interpreting the results of time-dependent EOM-CCSD simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Characterization of Solid-State Battery Materials Using Neutron Scattering Techniques

Advanced batteries require advanced characterization techniques, and neutron scattering is one of the most powerful experimental methods available for studying next-generation battery materials. Neutron scattering offers a non-destructive method to probe the complex structural and chemical processes occurring in batteries during operation in truly in situ/in operando measurements with a high sensitivity to battery-relevant elements such as lithium. Neutrons have energies comparable to the energies of excitations in materials and wavelengths comparable to atomic distances in the solid state, thus giving access to study structural and dynamical properties of materials on an atomic scale. In this review, a broad overview of selected neutron scattering techniques is presented to illustrate how neutron scattering can be used to gain invaluable information of solid-state battery materials, with a focus on in situ/in operando methods. These techniques span multiple decades of length and time scales to uncover the complex processes taking place fundamentally on the atomic scale and to determine how these processes impact the macroscale properties and performance of functional battery systems. This review serves the solid-state battery research community by examining how the unique capabilities of neutron scattering can be applied to answer critical and unresolved questions of materials research in this field. A thorough and broad perspective is provided with numerous practical examples showing these techniques in action for battery research.

25 ENERGY STORAGE↗

Excitation of millimeter and submillimeter water masers

The excitation of maser emission in millimeter and submillimeter transitions of interstellar and circumstellar water is considered. An escape probability method is used to determine the equilibrium populations in 349 rotational states of both ortho- and para-water under varying conditions of gas temperature, density, water abundance, and radiation field. It is shown that, under those conditions believed to prevail around late-type stars and within star-forming regions, strong millimeter and submillimeter water maser emission can be generated by collisional excitations by H2. Several maser transitions can have strengths close to that of the 22 GHz line. The water maser line which can be observed from mountaintop facilities and those which will require air- or space-borne platforms are indicated. The exact portion of parameter space in which each maser transition exhibits peak emission is shown.

Neufeld, David A.↗

Convergent close-coupling calculations of electron scattering on HeH +

Here, we use the molecular convergent close-coupling (MCCC) method to perform calculations of 10–1000 eV electron scattering on the ground state of HeH + . Cross sections are presented for excitation of the n = 2 – 3 singlet and triplet states (where n is the united-atoms-limit principle quantum number), as well as ionization. We also present cross sections for He + and H + ion production following dissociative excitation and ionization. The He + production cross section is compared with the measurements of Lecointre, Jureta, Urbain, and Defrance [J. Lecointre, J. J. Jureta, X. Urbain, and P. Defrance, J. Phys. B At. Mol. Opt. Phys. 47, 015203 (2014)]. We find that the MCCC results are up to 30% higher than experiment.

74 ATOMIC AND MOLECULAR PHYSICS↗

Stability of the particle-hole Pfaffian state and the 5 2 -fractional quantum Hall effect

Here we present a method for the exact construction of the fully particle-hole symmetric Pfaffian (PH-Pfaffian) ground state and its charged excitations on a sphere. We adopt the Moore-Read state, but with a nonholomorphic pairing component as in previous studies, and project it to the lowest Landau level. We study the energetics as well as other properties of these states and find that in a pure system interacting with the Coulomb forces the PH-Pfaffian cannot compete with either the Moore-Read state or its particle-hole conjugate, the anti-Pfaffian state, as an explanation for the 5/2 effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A modified coupled pair functional approach

A modified coupled pair functional (CPF) method is presented for the configuration interaction problem that dramatically improves properties for cases where the Hartree-Fock reference configuration is not a good zeroth-order wave function description. It is shown that the tendency for CPF to overestimate the effect of higher excitations arises from the choice of the geometric mean for the partial normalization denominator. The modified method is demonstrated for ground state dipole moment calculations of the NiH, CuH, and ZnH transition metal hydrides, and compared to singles-plus-doubles configuration interaction and the Ahlrichs et al. (1984) CPF method.

Chong, D. P.↗