Showing papers on "Ab initio quantum chemistry methods published in 2020"

Quantum simulations of materials on near-term quantum computers

Abstract: Quantum computers hold promise to enable efficient simulations of the properties of molecules and materials; however, at present they only permit ab initio calculations of a few atoms, due to a limited number of qubits. In order to harness the power of near-term quantum computers for simulations of larger systems, it is desirable to develop hybrid quantum-classical methods where the quantum computation is restricted to a small portion of the system. This is of particular relevance for molecules and solids where an active region requires a higher level of theoretical accuracy than its environment. Here, we present a quantum embedding theory for the calculation of strongly-correlated electronic states of active regions, with the rest of the system described within density functional theory. We demonstrate the accuracy and effectiveness of the approach by investigating several defect quantum bits in semiconductors that are of great interest for quantum information technologies. We perform calculations on quantum computers and show that they yield results in agreement with those obtained with exact diagonalization on classical architectures, paving the way to simulations of realistic materials on near-term quantum computers.

Quantum simulations of materials on near-term quantum computers

Abstract: Quantum computers hold promise to enable efficient simulations of the properties of molecules and materials; however, at present they only permit ab initio calculations of a few atoms, due to a limited number of qubits. In order to harness the power of near-term quantum computers for simulations of larger systems, it is desirable to develop hybrid quantum-classical methods where the quantum computation is restricted to a small portion of the system. This is of particular relevance for molecules and solids where an active region requires a higher level of theoretical accuracy than its environment. Here we present a quantum embedding theory for the calculation of strongly-correlated electronic states of active regions, with the rest of the system described within density functional theory. We demonstrate the accuracy and effectiveness of the approach by investigating several defect quantum bits in semiconductors that are of great interest for quantum information technologies. We perform calculations on quantum computers and show that they yield results in agreement with those obtained with exact diagonalization on classical architectures, paving the way to simulations of realistic materials on near-term quantum computers.

Insights into the complexity of the excited states of Eu-doped luminescent materials

Abstract: It has always been a spectroscopist's dream to correlate a material's luminescence properties with its microscopic structure, based on reliable structure–property relationships. Electronic structure methods are promising to achieve this goal; yet they are especially challenging in the case of Eu-based materials which are known to feature exceptionally high density of excited states, large spins and severe electron correlation. In this work, state-of-the-art multiconfigurational ab initio embedded-cluster methods are applied to gain a deeper insight into the luminescence mechanisms of Eu2+ and Eu3+-doped phosphors. Regardless of the difficulties, very accurate excitation energies are achieved, reaching 68% prediction intervals of 300 cm−1, corresponding to an accuracy of 5–10 nm in the visible wavelength range. Complete configurational coordinate curves are obtained, yielding breathing mode vibrational frequencies and equilibrium bond lengths for all excited states. Moreover, electric dipole transition moments and oscillator strengths are used to calculate absorption spectra. Excellent agreement with experiment is found. The ab initio calculations give an unprecedented detailed view of the Eu2+ excited state landscape, allowing for an improved understanding of its structure, including the origin of the so-called ‘staircase structure’ and the role of ligand covalency in the ligand field and exchange splitting. It is found that more covalent host compounds feature higher exchange splittings due to an increased stabilization of high-spin states by the interaction with virtual LMCT states. It is verified that the equilibrium Eu–ligand bond length contracts upon 4f–5d excitation towards the lowest 5d submanifold and that the bond lengths are directly related to the configurational character of the electronic eigenstate. Moreover, comparing ab initio calculations with crystal field calculations proves that a decoupled model for the Eu2+ excited states is inadequate, making the use of an intermediate coupling scheme compulsory. With this approach, computational design of luminescent materials is getting within reach.

Theory of the special displacement method for electronic structure calculations at finite temperature

Abstract: This work presents the theory of the special displacement method that enables computationally tractable ab initio calculations of the electronic and optical properties of solids at finite temperature. The authors demonstrate the capabilities of this method by reproducing thermal displacement ellipsoids measured by X-ray diffraction and temperature-dependent band structures of prototypical nonpolar and polar semiconductors, as well as a prototypical two-dimensional semiconductor.

Single‐Chain Magnet Based on Cobalt(II) Thiocyanate as XXZ Spin Chain

Abstract: The cobalt(II) in [Co(NCS)2 (4-methoxypyridine)2 ]n are linked by pairs of thiocyanate anions into linear chains. In contrast to a previous structure determination, two crystallographically independent cobalt(II) centers have been found to be present. In the antiferromagnetic state, below the critical temperature (Tc =3.94 K) and critical field (Hc =290 Oe), slow relaxations of the ferromagnetic chains are observed. They originate mainly from defects in the magnetic structure, which has been elucidated by micromagnetic Monte Carlo simulations and ac measurements using pristine and defect samples. The energy barriers of the relaxations are Δτ1 =44.9(5) K and Δτ2 =26.0(7) K for long and short spin chains, respectively. The spin excitation energy, measured by using frequency-domain EPR spectroscopy, is 19.1 cm-1 and shifts 0.1 cm-1 due to the magnetic ordering. Ab initio calculations revealed easy-axis anisotropy for both CoII centers, and also an exchange anisotropy Jxx /Jzz of 0.21. The XXZ anisotropic Heisenberg model (solved by using the density renormalization matrix group technique) was used to reconcile the specific heat, susceptibility, and EPR data.

Comparative Ab Initio Calculations of ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) Surfaces

Abstract: We performed, for first time, ab initio calculations for the ReO2-terminated ReO3 (001) surface and analyzed systematic trends in the ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surfaces using first-principles calculations. According to the ab initio calculation results, all ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface upper-layer atoms relax inwards towards the crystal bulk, all second-layer atoms relax upwards and all third-layer atoms, again, relax inwards. The ReO2-terminated ReO3 and ZrO2-terminated SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface band gaps at the Γ–Γ point are always reduced in comparison to their bulk band gap values. The Zr–O chemical bond populations in the SrZrO3, BaZrO3, PbZrO3 and CaZrO3 perovskite bulk are always smaller than those near the ZrO2-terminated (001) surfaces. In contrast, the Re–O chemical bond population in the ReO3 bulk (0.212e) is larger than that near the ReO2-terminated ReO3 (001) surface (0.170e). Nevertheless, the Re–O chemical bond population between the Re atom located on the ReO2-terminated ReO3 (001) surface upper layer and the O atom located on the ReO2-terminated ReO3 (001) surface second layer (0.262e) is the largest.

Long-range quadrupole electron-phonon interaction from first principles

Abstract: Lattice vibrations in materials induce perturbations on the electron dynamics in the form of long-range (dipole and quadrupole) and short-range (octopole and higher) potentials. The dipole Fr\"ohlich term can be included in current first-principles electron-phonon (e-ph) calculations and is present only in polar materials. The quadrupole e-ph interaction is present in both polar and nonpolar materials, but currently it cannot be computed from first principles. Here we show an approach to compute the quadrupole e-ph interaction and include it in ab initio calculations of e-ph matrix elements. The accuracy of the approach is demonstrated by comparing with direct density functional perturbation theory calculations. We apply our method to silicon as a case of a nonpolar semiconductor and tetragonal ${\mathrm{PbTiO}}_{3}$ as a case of a polar piezoelectric material. In both materials we find that the quadrupole term strongly impacts the e-ph matrix elements. Analysis of e-ph interactions for different phonon modes reveals that the quadrupole term mainly affects optical modes in silicon and acoustic modes in ${\mathrm{PbTiO}}_{3}$, although the quadrupole term is needed for all modes to achieve quantitative accuracy. The effect of the quadrupole e-ph interaction on electron scattering processes and transport is shown to be important. Our approach enables accurate studies of e-ph interactions in broad classes of nonpolar, polar, and piezoelectric materials.

Ab Initio Computation of Charge Densities for Sn and Xe Isotopes

Abstract: We present the first ab initio calculations for open-shell nuclei past the tin isotopic line, focusing on Xe isotopes as well as doubly magic Sn isotopes. We show that, even for moderately hard interactions, it is possible to obtain meaningful predictions and that the ${\mathrm{NNLO}}_{\mathrm{sat}}$ chiral interaction predicts radii and charge density distributions close to the experiment. We then make a new prediction for $^{100}\mathrm{Sn}$. This paves the way for ab initio studies of exotic charge density distributions at the limit of the present ab initio mass domain, where experimental data is becoming available. The present study closes the gap between the largest isotopes reachable by ab initio methods and the smallest exotic nuclei accessible to electron scattering experiments.

Ab initio electron-two-phonon scattering in GaAs from next-to-leading order perturbation theory.

Abstract: Electron-phonon (e–ph) interactions are usually treated in the lowest order of perturbation theory. Here we derive next-to-leading order e–ph interactions, and compute from first principles the associated electron-two-phonon (2ph) scattering rates. The derivations involve Matsubara sums of two-loop Feynman diagrams, and the numerical calculations are challenging as they involve Brillouin zone integrals over two crystal momenta and depend critically on the intermediate state lifetimes. Using Monte Carlo integration together with a self-consistent update of the intermediate state lifetimes, we compute and converge the 2ph scattering rates, and analyze their energy and temperature dependence. We apply our method to GaAs, a weakly polar semiconductor with dominant optical-mode long-range e–ph interactions. We find that the 2ph scattering rates are as large as nearly half the value of the one-phonon rates, and that including the 2ph processes is necessary to accurately predict the electron mobility in GaAs from first principles. Electron-phonon scattering plays a decisive role in electron transport and is taken into account in ab initio calculations by leading-order perturbations involving scattering events with one phonon. Here, the authors show that higher-order effects are comparable in magnitude to the leading order in polar semiconductors.

Anharmonic multi-phonon nonradiative transition: An ab initio calculation approach

Abstract: Nonradiative carrier recombinations at deep centers in semiconductors are of great importance for both fundamental physics and device engineering. In this article, we provide a revised analysis of Huang’s original nonradiative multi-phonon (NMP) theory with ab initio calculations. First, we confirmed at the first-principles level that Huang’s concise formula gives the same results as the matrix-based formula, and that Huang’s high-temperature formula provides an analytical expression for the coupling constant in Marcus theory. Secondly, we correct for anharmonic effects by taking into account local phonon-mode variations for different charge states of a defect. The corrected capture rates for defects in GaN and SiC agree well with experiments.

Four Dinuclear and One-Dimensional-Chain Dysprosium and Terbium Complexes Based on 2-Hydroxy-3-methoxybenzoic Acid: Structures, Fluorescence, Single-Molecule-Magnet, and Ab Initio Investigation.

Abstract: The unique electronic configurations of lanthanide(III) ions generate abundant electronic energy levels, resulting in the fantastic magnetic and optical multifunctional properties of lanthanide com...

Ab Initio Calculations of Free Energy of Activation at Multiple Electronic Structure Levels Made Affordable: An Effective Combination of Perturbation Theory and Machine Learning.

Abstract: While free energies are fundamental thermodynamic quantities to characterize chemical reactions, their calculation based on ab initio theory is usually limited by the high computational cost. This ...

Structural, electronic, magnetic and thermoelectric properties of Full-Heusler Fe2MnSi: Ab initio calculations

Abstract: The linear wave augmented plane waves method at full potential using the functional density theory and applying the approximation methods “GGA-PBE, PBE-sol, mBJ and GGA + U” has been used to investigate the electronic, thermoelectric, magnetic and transport properties of Full-Heusler F e 2 M n S i . The optimized and the most stable crystal structure at equilibrium is face-centered cubic with space group and lattice parameters a = 5.591 A. The half metallic character is observed with an indirect band gap. To determine the stability of this material, the elastic parameters have been computed. Moreover, the Seebeck coefficients and the electrical conductivity have been obtained. It is found that the spin polarization (SP) reaches 100% for F e 2 M n S i due to its half metallic state.

High Activity toward the Hydrogen Evolution Reaction on the Edges of MoS2-Supported Platinum Nanoclusters Using Cluster Expansion and Electrochemical Modeling

Abstract: The design of efficient and cost-effective platinum-based catalysts for the hydrogen evolution reaction (HER) is critical for energy sustainability. Herein, we report high catalytic activity toward HER on the edges of platinum nanoclusters (NCs) supported on single-layer molybdenum disulfide and provide a direct link between ab initio calculations and electrochemical experiments. We determine the active catalytic sites using a cluster expansion method in conjunction with an ab initio thermodynamic approach and show that the system is thermodynamically active at HER reversible potential under electrochemical conditions. We also show that the preferred HER mechanism is the Volmer–Tafel pathway with the Volmer reaction as the rate-determining step. Using a Butler–Volmer kinetic model to simulate a linear sweep voltammogram, we obtain an exchange current density of 10–3–10–2 A/cm2, which is in the same order as those measured for Pt(111) and supported Pt NCs. Importantly, we show that, contrary to expectation...

H 2 -He collisions: Ab initio theory meets cavity-enhanced spectra

Abstract: Fully quantum ab initio calculations of the collision-induced shapes of two rovibrational ${\mathrm{H}}_{2}$ lines perturbed by He provide an unprecedented subpercent agreement with ultra-accurate cavity-enhanced measurements. This level of consistency between theory and experiment hinges on a highly accurate potential energy surface and a realistic treatment of the velocity changing and dephasing collisions. In addition to the fundamental importance, these results show that ab initio calculations can provide reference data for spectroscopic studies of planet atmospheres at the required accuracy level and can be used to populate spectroscopic line-by-line databases.

Discovery of HC3O+ in space: The chemistry of O-bearing species in TMC-1

Abstract: Using the Yebes 40m and IRAM 30m radio telescopes, we detected a series of harmonically related lines with a rotational constant B0=4460.590 +/- 0.001 MHz and a distortion constant D0=0.511 +/- 0.005 kHz towards the cold dense core TMC-1. High-level-of-theory ab initio calculations indicate that the best possible candidate is protonated tricarbon monoxide, HC3O+. We have succeeded in producing this species in the laboratory and observed its J = 2-1 and 3-2 rotational transitions. Hence, we report the discovery of HC3O+ in space based on our observations, theoretical calculations, and laboratory experiments. We derive an abundance ratio N(C3O)/N(HC3O+) = 7. The high abundance of the protonated form of C3O is due to the high proton affinity of the neutral species. The chemistry of O-bearing species is modelled, and predictions are compared to the derived abundances from our data for the most prominent O-bearing species in TMC-1.

Ab initio modelling of local interfaces in doped organic semiconductors

Abstract: Doping in organic semiconductors remains a debated issue from both an experimental and ab initio perspective. Due to the complexity of these systems, which exhibit a low degree of crystallinity and high level of disorder, modelling doped organic semiconductors from first-principles calculations is not a trivial task, as their electronic and optical properties are sensitive to the choice of initial geometries. A crucial aspect to take into account, in view of rationalizing the electronic structure of these materials through ab initio calculations, is the role of local donor/acceptor interfaces. We address this problem in the framework of state-of-the-art density-functional theory and many-body perturbation theory, investigating the structural, electronic, and optical properties of quaterthiophene and sexithiophene oligomers doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ). We consider different model structures ranging from isolated dimers and trimers, to periodic stacks. Our results demonstrate that the choice of the initial geometry critically impacts the resulting electronic structure and the degree of charge transfer in the materials, depending on the amount and on the nature of the local interfaces between donor and acceptor species. The optical spectra appear less sensitive to these parameters at least from a first glance, although a quantitative analysis of the excitations reveals that their Frenkel or charge-transfer character is affected by the characteristics of the donor/acceptor interfaces as well as by the donor length. Our findings represent an important step forward towards an insightful first-principles description of the microscopic properties of doped organic semiconductors complementary to experiments.

Gaussian process model of 51-dimensional potential energy surface for protonated imidazole dimer.

Abstract: The goal of the present work is to obtain accurate potential energy surfaces (PESs) for high-dimensional molecular systems with a small number of ab initio calculations in a system-agnostic way. We use probabilistic modeling based on Gaussian processes (GPs). We illustrate that it is possible to build an accurate GP model of a 51-dimensional PES based on 5000 randomly distributed ab initio calculations with a global accuracy of 20 000 cm−1). This opens the prospect for new applications of GPs, such as mapping out phase transitions by extrapolation or accelerating Bayesian optimization, for high-dimensional physics and chemistry problems with a restricted number of inputs, i.e., for high-dimensional problems where obtaining training data is very difficult.

Non-Boltzmann vibrational energy distributions and coupling to dissociation rate

Abstract: In this article, we propose a generalized model for nonequilibrium vibrational energy distribution functions. The model can be used, in place of equilibrium (Boltzmann) distribution functions, when deriving reaction rate constants for high-temperature nonequilibrium flows. The distribution model is derived based on the recent ab initio calculations, carried out using potential energy surfaces developed using accurate computational quantum chemistry techniques for the purpose of studying air chemistry at high temperatures. Immediately behind a strong shock wave, the vibrational energy distribution is non-Boltzmann. Specifically, as the gas internal energy rapidly excites to a high temperature, overpopulation of the high-energy tail (relative to a corresponding Boltzmann distribution) is observed in ab initio simulations. As the gas excites further and begins to dissociate, a depletion of the high-energy tail is observed, during a time-invariant quasi-steady state. Since the probability of dissociation is exponentially related to the vibrational energy of the dissociating molecule, the overall dissociation rate is sensitive to the populations of these high vibrational energy states. The non-Boltzmann effects captured by the new model either enhance or reduce the dissociation rate relative to that obtained assuming a Boltzmann distribution. This article proposes a simple model that is demonstrated to reproduce these non-Boltzmann effects quantitatively when compared to ab initio simulations.

An approach to estimate the barrier height for magnetisation reversal in {Dy2} SMMs using ab initio calculations

Abstract: Although ab initio CASSCF calculations yield a good numerical estimate of barrier height for magnetisation reversal for mononuclear Dy(III) SIMs, obtaining a reliable value for higher nuclearity clusters such as {Dy2} are challenging. By analysing ab initio computed data of thirty-one different {Dy2} SMMs, we propose a model equation that relates the calculated barrier heights to the experimental values and offers a viable way to predict the barrier heights in {Dy2} SMMs.

Ab initio calculations of CaZrO3 (011) surfaces: systematic trends in polar (011) surface calculations of ABO3 perovskites

Abstract: By means of the CRYSTAL computer program package, first-principles calculations of polar ZrO-, Ca- and O-terminated CaZrO3 (011) surfaces were performed. Our calculation results for polar CaZrO3 (011) surfaces are compared with the previous ab initio calculation results for ABO3 perovskite (011) and (001) surfaces. From the results of our hybrid B3LYP calculations, all upper-layer atoms on the ZrO-, Ca- and O-terminated CaZrO3 (011) surfaces relax inwards. The only exception from this systematic trend is outward relaxation of the oxygen atom on the ZrO-terminated CaZrO3 (011) surface. Different ZrO, Ca and O terminations of the CaZrO3 (011) surface lead to a quite different surface energies of 3.46, 1.49, and 2.08 eV. Our calculations predict a considerable increase in the Zr–O chemical bond covalency near the CaZrO3 (011) surface, both in the directions perpendicular to the surface (0.240e) as well as in the plane (0.138e), as compared to the CaZrO3 (001) surface (0.102e) and to the bulk (0.086e). Such increase in the B–O chemical bond population from the bulk towards the (001) and especially (011) surfaces is a systematic trend in all our eight calculated ABO3 perovskites.

Improvement of Ab Initio Ligand Field Theory by Means of Multistate Perturbation Theory

Abstract: Over the last few years, ab initio ligand field theory (AILFT) has evolved into an important tool for the extraction of ligand field models from ab initio calculations. The inclusion of dynamic correlation on top of complete active space self-consistent field (CASSCF) reference functions, which is important for accurate results, was so far realized at the level of second-order N-electron valence state perturbation theory (NEVPT2). In this work, we introduce two alternative methods for the inclusion of dynamic correlation into AILFT calculations, the second-order dynamic correlation dressed complete active space method (DCD-CAS(2)) and the Hermitian quasi-degenerate NEVPT2 (HQD-NEVPT2). These methods belong to the class of multistate perturbation theory approaches, which allow for the mixing of CASSCF states under the effect of dynamic correlation (state-mixing). The two new versions of AILFT were tested for a diverse set of transition-metal complexes. It was found that the multistate methods have, compared to NEVPT2, an AILFT fit with smaller root mean square deviations (rmsds) between ab initio and AILFT energies. A comparison of AILFT excitation energies with the experiment shows that for some systems, the agreement gets better at the multistate level because of the smaller rmsds. However, for some systems, the agreement gets worse, which could be attributed to a cancellation of errors at the NEVPT2 level that is partly removed at the multistate level. An investigation of trends in the extracted ligand field parameters shows that at the multistate level, the ligand field splitting Δ gets larger, whereas the Racah parameters B and C get smaller and larger, respectively. An investigation of the reasons for the observed improvement for octahedral CrIII halide complexes shows that the possibility of state-mixing relaxes constraints that are present at the NEVPT2 level and that keep Δ and B from following their individual preferences.