Ab Initio Quantum Molecular Dynamics Research Articles

Towards atomistic modelling of solid Pb-O formation and dissolution in liquid lead coolant: Interatomic potential development

Microscopic description of solid Pb-O formation and dissolution in liquid lead coolant is important for the modelling of fast neutron reactors. For this purpose, in this work we develop interatomic potential models for lead melt with dissolved oxygen. Potentials fitting is based on ab initio density functional theory (DFT) calculations and quantum molecular dynamics. Two different potential models are trained on the DFT data using the force-matching method: a computationally cheap embedded atom method (EAM) potential and a computationally expensive machine-learned moment tensor potential (MTP) that allows reproducing DFT data very accurately. The potentials are further validated to reproduce the properties of lead melt and the coordination of oxygen atoms in molten lead. The diffusion coefficient for oxygen in molten lead is calculated and compared with the available experimental data. We analyse how these interatomic potential models describe the crystal structure of the solid lead oxide to consider PbO nucleation and dissolution in molten lead. We extensively discuss the arising problems with the description of long-range electrostatic interactions. The possibility of matching the experimental data on the oxygen solubility limit by tuning the EAM potential is shown.

Palladium at high pressure and high temperature: A combined experimental and theoretical study

Palladium is one of the most important technological materials, yet its phase diagram remains poorly understood. At ambient conditions, its solid phase is face-centered cubic (fcc). However, another solid phase of Pd, body-centered cubic (bcc), was very recently predicted in two independent theoretical studies to occur at high pressures and temperatures. In this work, we report an experimental study on the room-temperature equation of state (EOS) of Pd to a pressure of 80 GPa, as well as a theoretical study on the phase diagram of Pd including both fcc-Pd and bcc-Pd. Our theoretical approach consists in ab initio quantum molecular dynamics (QMD) simulations based on the Z methodology which combines both direct Z method for the simulation of melting curves and inverse Z method for the calculation of solid–solid phase transition boundaries. We obtain the melting curves of both fcc-Pd and bcc-Pd and an equation for the fcc–bcc solid–solid phase transition boundary as well as the thermal EOS of Pd which is in agreement with experimental data and QMD simulations. We uncover the presence of another solid phase of Pd on its phase diagram, namely, random hexagonal close-packed (rhcp), and estimate the location of the rhcp-bcc solid–solid phase transition boundary and the rhcp–fcc–bcc triple point. We also discuss the topological similarity of the phase diagrams of palladium and silver, the neighbor of Pd in the periodic table. We argue that Pd is a reliable standard for shock-compression studies and present the analytic model of its principal Hugoniot in a wide pressure range.

Ab Initio Phase Diagram of Chromium to 2.5 TPa

Chromium possesses remarkable physical properties such as hardness and corrosion resistance. Chromium is also a very important geophysical material as it is assumed that lighter Cr isotopes were dissolved in the Earth’s molten core during the planet’s formation, which makes Cr one of the main constituents of the Earth’s core. Unfortunately, Cr has remained one of the least studied 3d transition metals. In a very recent combined experimental and theoretical study (Anzellini et al., Scientific Reports, 2022), the equation of state and melting curve of chromium were studied to 150 GPa, and it was determined that the ambient body-centered cubic (bcc) phase of crystalline Cr remains stable in the whole pressure range considered. However, the importance of the knowledge of the physical properties of Cr, specifically its phase diagram, necessitates further study of Cr to higher pressure. In this work, using a suite of ab initio quantum molecular dynamics (QMD) simulations based on the Z methodology which combines both direct Z method for the simulation of melting curves and inverse Z method for the calculation of solid–solid phase transition boundaries, we obtain the theoretical phase diagram of Cr to 2.5 TPa. We calculate the melting curves of the two solid phases that are present on its phase diagram, namely, the lower-pressure bcc and the higher-pressure hexagonal close-packed (hcp) ones, and obtain the equation for the bcc-hcp solid–solid phase transition boundary. We also obtain the thermal equations of state of both bcc-Cr and hcp-Cr, which are in excellent agreement with both experimental data and QMD simulations. We argue that 2180 K as the value of the ambient melting point of Cr which is offered by several public web resources (“Wikipedia,” “WebElements,” “It’s Elemental,” etc.) is most likely incorrect and should be replaced with 2135 K, found in most experimental studies as well as in the present theoretical work.

Ab initio phase diagram of silver

Silver has been considered as one of the simple one-phase materials that do not exhibit high pressure or high temperature polymorphism. The solid phase of Ag at ambient conditions is face-centered cubic (fcc) one. However, very recently another solid phase of silver, body-centered cubic (bcc) one, was detected in shock-wave (SW) experiments, and a more sophisticated phase diagram of Ag with the two solid phases was published by Smirnov. In this work, using a suite of ab initio quantum molecular dynamics (QMD) simulations based on the Z methodology which combines both direct Z method for the simulation of melting curves and inverse Z method for the calculation of solid–solid phase boundaries, we refine the phase diagram of Smirnov. We calculate the melting curves of both fcc-Ag and bcc-Ag and obtain an equation for the fcc–bcc solid–solid phase transition boundary. We also obtain the thermal equation of state of Ag which is in agreement with experimental data and QMD simulations. We argue that, despite being a polymorphic rather than a simple one-phase material, silver can be considered as an SW standard.

Ab Initio Phase Diagram of Copper

Copper has been considered as a common pressure calibrant and equation of state (EOS) and shock wave (SW) standard, because of the abundance of its highly accurate EOS and SW data, and the assumption that Cu is a simple one-phase material that does not exhibit high pressure (P) or high temperature (T) polymorphism. However, in 2014, Bolesta and Fomin detected another solid phase in molecular dynamics simulations of the shock compression of Cu, and in 2017 published the phase diagram of Cu having two solid phases, the ambient face-centered cubic (fcc) and the high-PT body-centered cubic (bcc) ones. Very recently, bcc-Cu has been detected in SW experiments, and a more sophisticated phase diagram of Cu with the two solid phases was published by Smirnov. In this work, using a suite of ab initio quantum molecular dynamics (QMD) simulations based on the Z methodology, which combines both direct Z method for the simulation of melting curves and inverse Z method for the calculation of solid–solid phase boundaries, we refine the phase diagram of Smirnov. We calculate the melting curves of both fcc-Cu and bcc-Cu and obtain an equation for the fcc-bcc solid–solid phase transition boundary. We also obtain the thermal EOS of Cu, which is in agreement with experimental data and QMD simulations. We argue that, despite being a polymorphic rather than a simple one-phase material, copper remains a reliable pressure calibrant and EOS and SW standard.

Directing excited state dynamics via chemical substitution: A systematic study of π-donors and π-acceptors at a carbon-carbon double bond.

Functional group substituents are a ubiquitous tool in ground-state organic chemistry often employed to fine-tune chemical properties and obtain desired chemical reaction outcomes. Their effect on photoexcited electronic states, however, remains poorly understood. To help build an intuition for these effects, we have studied ethylene, substituted with electron acceptor (cyano) and/or electron donor (methoxy) substituents, both theoretically and experimentally: using ab initio quantum molecular dynamics and time-resolved photoelectron spectroscopy. Our results show the consistent trend that photo-induced ethylenic dynamics is primarily localized to the carbon with the greater electron density. For doubly substituted ethylenes, the trend is additive when both substituents are located on opposite carbons, whereas the methoxy group (in concert with steric effects) dominates when both substituents are located on a single carbon atom. These results point to the development of rules for structure-dynamics correlations; in this case, a novel mechanistic ultrafast photochemistry for conjugated carbon chains employing long-established chemical concepts.

Progress towards nanoengineered energetic materials

Given the constraints on typical bond energies and the commonality of final products produced from combustion of CHNO based energetic materials, the possibilities for further increases in stored potential energy and thermodynamic performance from these classes of materials are limited. Thus, modulating the energy release to achieve efficiency and effectiveness for desired applications is of great value. Investigation of nanomaterials as energetic materials began more than twenty years ago with much of the interest to increase reaction rates and reduce sensitivity. During this period, research on energetic nanoparticles was devoted to reducing the loss of energy density with metallic materials due to the naturally occurring oxide passivating layer, managing their high surface area preventing high loadings in solids, minimizing particle-particle interactions making dispersion in the gas-phase difficult, and understanding combustion mechanisms. As an outcome, novel synthesis methods of producing nanocomposites, and new fields of applications, such as micro-pyrotechnics, have developed. Yet, the research community is only beginning to understand how to manipulate and build energetic materials at the nanoscale, and what designs are optimal for desired functions. Furthermore, recognizing the difficulties for increased energy density and reduced sensitivity, the development of multifunctional and smart nanoenergetic materials is currently being researched to enable control of energy release rates and material sensitivity on demand. This research is being advanced by assembly of nanoengineered energetic materials to bulk scales by additive manufacturing, the development and application of combustion diagnostics that resolve nanometer and micron scales, and ab initio quantum chemistry and molecular dynamics calculations. The challenges that have been confronted and the directions of continuing research on nanoenergetics are presented and discussed.

Experimental and theoretical confirmation of an orthorhombic phase transition in niobium at high pressure and temperature

Compared to other body-centered cubic (bcc) transition metals, Nb has been the subject of fewer compression studies and there are still aspects of its phase diagram which are unclear. Here, we report a combined theoretical and experimental study of Nb under high pressure and temperature. We present the results of static laser-heated diamond anvil cell experiments up to 120 GPa using synchrotron-based fast x-ray diffraction combined with ab initio quantum molecular dynamics simulations. The melting curve of Nb is determined and evidence for a solid-solid phase transformation in Nb with increasing temperature is found. The high-temperature phase of Nb is orthorhombic Pnma. The bcc-Pnma transition is clearly seen in the experimental data on the Nb principal Hugoniot. The bcc-Pnma coexistence observed in our experiments is explained. Agreement between the measured and calculated melting curves is very good except at 40–60 GPa where three experimental points lie below the theoretical melting curve by 250 K (or 7%); a possible explanation is given.

Generation of Amorphous Silicon Dioxide Structures via Melting-Quenching Density Functional Modeling

Ab initio quantum molecular dynamics simulation is used to transform a silicon dioxide crystal into silica amorphous states. Two type of amorphous states are obtained from the melts stabilized at temperatures well above the crystal melting point. The first type of amorphous states are obtained from the melts stabilized at comparably low temperatures of $$3000$$ and $$4000$$ K. These states are characterized by a perfect structure similar to those of the initial crystal and vitreous silica glass without point defects. Completely different amorphous states are obtained from the high temperature melts of $$5000$$ and $$6000$$ K. Structures of these amorphous states are less regular and contain point defects of silicon dioxide such as over-coordinated fivefold silicon, threefold oxygen atoms and a new silica defect 2-Bridging Oxygen Center. The latter is detected in the model of amorphous silica for the first time and it is formed by two neighbouring $$SiO_{4}$$ -tetrahedra with two common oxygen vertexes. The amorphous silica models can be useful for description of amorphous silicon dioxide films obtained by high energy ion-beam deposition process where a fast local melting-quenching process should exist.

A new set of atmosphere and evolution models for cool T–Y brown dwarfs and giant exoplanets

We present a new set of solar metallicity atmosphere and evolutionary models for very cool brown dwarfs and self-luminous giant exoplanets, which we term ATMO 2020. Atmosphere models are generated with our state-of-the-art 1D radiative-convective equilibrium code ATMO, and are used as surface boundary conditions to calculate the interior structure and evolution of 0.001–0.075 M⊙ objects. Our models include several key improvements to the input physics used in previous models available in the literature. Most notably, the use of a new H–He equation of state including ab initio quantum molecular dynamics calculations has raised the mass by ~1−2% at the stellar–substellar boundary and has altered the cooling tracks around the hydrogen and deuterium burning minimum masses. A second key improvement concerns updated molecular opacities in our atmosphere model ATMO, which now contains significantly more line transitions required to accurately capture the opacity in these hot atmospheres. This leads to warmer atmospheric temperature structures, further changing the cooling curves and predicted emission spectra of substellar objects. We present significant improvement for the treatment of the collisionally broadened potassium resonance doublet, and highlight the importance of these lines in shaping the red-optical and near-infrared spectrum of brown dwarfs. We generate three different grids of model simulations, one using equilibrium chemistry and two using non-equilibrium chemistry due to vertical mixing, all three computed self-consistently with the pressure-temperature structure of the atmosphere. We show the impact of vertical mixing on emission spectra and in colour-magnitude diagrams, highlighting how the 3.5−5.5 μm flux window can be used to calibrate vertical mixing in cool T–Y spectral type objects.

Compression of liquid Ni and Co under extreme conditions explored by x-ray absorption spectroscopy

The compression of liquid nickel and cobalt has been investigated up to 102 and 83 GPa, respectively, by x-ray absorption spectroscopy at the Ni and Co $K$ edges, using laser-heated diamond anvil cell. A shortening of about 8%--10% of the metal bond distances is observed in the pressure range considered and the experimental results are confirmed by theoretical calculations. Ab initio quantum molecular dynamics calculations have been performed, providing a model pair distribution function for cobalt, used as a starting model in the extended x-ray absorption fine structure analysis. The specific volume of the liquid has also been estimated and compared to calculations in the literature. This work sets the basis for x-ray absorption spectroscopy studies of liquid metals under extreme conditions with potentially important implications for the understanding of Earth and planetary interiors.

Dynamic polarity of curved aromatic soot precursors

In this paper, we answer the question of whether polar curved aromatics are persistently polar at flame temperatures. We find, using electronic structure calculations and transition state theory, that the inversion barriers of curved aromatics (cPAH) 0.9–1.2 nm in diameter are high and that they are not able to invert over the timescales and at the high temperatures found in sooting flames. We find a transition for smaller curved aromatics between 11–15 ( ≈ 0.8 nm) rings where the increasing strain introduced from the pentagonal ring increases the inversion barrier leading to rigidity. We then performed ab initio quantum molecular dynamics to find the molecular dipole fluctuations of a nanometre sized cPAH at 1500 K. We found the bending mode of the bowl shaped molecule gave rise to the largest fluctuations on the dipole moment by ± 0.5–1 debye about the equilibrium value of 5.00 debye, indicating persistent polarity. We also observed binding of a chemi-ion at 1500 K over 2 ps, suggesting the molecular dipole of cPAH will be an important consideration in soot formation mechanisms.

About the Aromaticity of symm-Triaminotrinitrobenzene.

Aromaticity and structural features of the isolated symm-triaminotrinitrobenzene (TATB) were examined using the nonempirical ab initio quantum chemical method and molecular dynamics at the Car-Parrinello level. Different criteria of the aromaticity were combined with the study of conformational flexibility of molecule and analysis of the electron density distribution. It was found that the cooperative effect of the resonance-assisted hydrogen bonds results in the ultimate decreasing aromaticity of the benzene ring in TATB. Values of the HOMA index indicate that it could be classified as low-aromatic in equilibrium state at zero temperature but completely nonaromatic at room temperature. An extremely high flexibility of the molecule is also not typical for aromatic rings. The electron delocalization in H-bonded O═N-C═C-N-H quasi-aromatic rings was found to be greater than that in the benzene ring of TATB.

A New Equation of State for Dense Hydrogen–Helium Mixtures

Abstract We present a new equation of state (EOS) for dense hydrogen/helium mixtures that covers a range of densities from 10−8 to , pressures from 10−9 to 1013 GPa, and temperatures from 102 to 108 K. The calculations combine the EOS of Saumon, Chabrier & van Horn in the low-density, low-temperature molecular/atomic domain, the EOS of Chabrier & Potekhin in the high-density, high-temperature fully ionized domain, the limits of which differ for H and He, and ab initio quantum molecular dynamics calculations in the regime of intermediate density and temperature, characteristic of pressure dissociation and ionization. The EOS for the H/He mixture is based on the so-called additive volume law and thus does not take into account the interactions between the two species. A major improvement of the present calculations over existing ones is that we calculate the entropy over the entire density–temperature domain, a necessary quantity for calculations of stellar or planetary evolution. The EOS results are compared with existing experimental data, namely Hugoniot shock experiments for pure H and He, and with first-principles numerical simulations for both the single elements and the mixture. This new EOS covers a wide range of physical and astrophysical conditions, from Jovian planets to solar-type stars, and recovers the existing relativistic EOS at very high densities, in the domains of white dwarfs and neutron stars. All the tables are made publicly available.

Studying the Urtica dioica leaves extract inhibition effect on the mild steel corrosion in 1 M HCl solution: Complementary experimental, ab initio quantum mechanics, Monte Carlo and molecular dynamics studies

Finding a cheap and green source of corrosion inhibitor has become an attractive area of research in recent years. Although there are a large number of reports on the application of plant extracts as a powerful source of corrosion inhibitors for metals in acidic media but most of them are not readily available and cost-effective. Thus, it would not be economically acceptable to use them in industrial applications. The second is that ethanol should be frequently used during the inhibitors extraction process, making the process environmentally unacceptable. In addition, the organic molecules present in the extracts of most of the plants only include oxygen containing groups that cannot be easily protonated in acidic media. In this study, Urtica dioica leaves have been introduced as a unique source of invaluable and unique chemical compounds like histamine and serotonin, which are known as important biocompatible and biologically active molecules. Urtica dioica is a wildflower type of plant that growths in large scale, therefore, it is a low cost source of green inhibitors. The extract of Urtica dioica includes nitrogen containing groups that can be easily protonated in the acidic media and shows high inhibition action.The effectiveness of the Urtica dioica leaves toward mild steel corrosion inhibition in 1 M HCl solution was studied by electrochemical impedance spectroscopy (EIS), polarization test, scanning electron microscope (SEM), atomic force microscope (AFM) and computational approaches. Results revealed that the extract of Urtica dioica showed mixed inhibition effect and its adsorption on the mild steel surface obeyed a Langmuir adsorption isotherm. In addition, a high corrosion inhibition efficiency of 92% was obtained for this inhibitor after 2 h immersion. This inhibitor also yielded high inhibition power even after a long immersion time (24 h), indicating the higher effectiveness of Urtica dioica compared with those reported in literature. It was observed that the corrosion rate of steel in 1 M HCl solution remarkably decreased in the presence of Urtica dioica extract. The computational results elucidated from the Monte Carlo and molecular dynamics simulations evidenced the adsorption of green inhibitors on the steel substrate. Furthermore, the density functional theory calculations suggested the inhibitors adsorption via electronic donor-acceptor interactions.

Multiscale Investigation of Femtosecond Laser Pulses Processing Aluminum in Burst Mode

ABSTRACTMegahertz is the highest femtosecond laser repetition rate that the state-of-the art technology can achieve. In this article, a single femtosecond laser pulse is burst into multiple femtosecond laser pulses to process aluminum. The temporal gap between two consecutive burst pulses is 2 picoseconds, which is much shorter than the temporal gap between two consecutive pulses at the repetition rate of megahertz. By taking the thermophysical scenarios of femtosecond laser induced of electron thermalization, electron heat conduction, electron–phonon-coupled heat transfer and atomic motion into account, a multiscale framework integrating ab initio quantum mechanical calculation, molecular dynamics and two-temperature model are constructed. The effect of femtosecond laser pulse number on the incubation phenomenon is studied. Comparing with the single pulse-processing aluminum film, the femtosecond laser in burst mode leads to smaller thermal stress, which is favorable to reduce the thermal mechanical damage of the material beneath the laser-irradiated surface. Appreciable differences among the simulation results by using electron thermophysical parameters from ab initio quantum mechanical calculation and those from experimental measurement, empirical estimation and calculation are found, indicating the essentials to precisely model the electron thermal response subject to femtosecond laser excitation.

Systematics of the Third Row Transition Metal Melting: The HCP Metals Rhenium and Osmium

The melting curves of rhenium and osmium to megabar pressures are obtained from an extensive suite of ab initio quantum molecular dynamics (QMD) simulations using the Z method. In addition, for Re, we combine QMD simulations with total free energy calculations to obtain its phase diagram. Our results indicate that Re, which generally assumes a hexagonal close-packed (hcp) structure, melts from a face-centered cubic (fcc) structure in the pressure range 20–240 GPa. We conclude that the recent DAC data on Re to 50 GPa in fact encompass both the true melting curve and the low-slope hcp-fcc phase boundary above a triple point at (20 GPa, 4240 K). A linear fit to the Re diamond anvil cell (DAC) data then results in a slope that is 2.3 times smaller than that of the actual melting curve. The phase diagram of Re is topologically equivalent to that of Pt calculated by us earlier on. Regularities in the melting curves of Re, Os, and five other 3rd-row transition metals (Ta, W, Ir, Pt, Au) form the 3rd-row transition metal melting systematics. We demonstrate how this systematics can be used to estimate the currently unknown melting curve of the eighth 3rd-row transition metal Hf.

Ab Initio Nonadiabatic Quantum Molecular Dynamics.

The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born-Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump-probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.

Screening the anti-corrosion effect of a hybrid pigment based on zinc acetyl acetonate on the corrosion protection performance of an epoxy-ester polymeric coating

In this study an epoxy-ester coating was filled with zinc acetyl acetonate (ZnAA). The active corrosion inhibition properties of the ZnAA pigment were studied by electrochemical noise (EN), electrochemical impedance spectroscopy (EIS) and polarization techniques. Also, the surface morphology and composition of the steel panels were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The electrochemical measurements revealed the effective corrosion inhibition properties of the ZnAA pigment in the solution phase. Polarization test results revealed that in the presence of ZnAA both cathodic and anodic current densities decreased. In fact, the Zn2+ cations and acetyl acetonate anions formed inhibitive films based on Fe2+-acetyl acetonate and zinc oxide/hydroxide complexes on the anodic and cathodic regions. Results of theoretical ab initio quantum mechanics and molecular dynamics simulations evidenced that the inhibitors strongly adsorbed to iron surface through donor–acceptor interactions. The EIS results showed that the epoxy-ester coating protection performance was significantly enhanced by addition of ZnAA hybrid pigment. The ZnAA pigment enhanced the barrier performance of the coating and provided active inhibition properties.

Directly probing anisotropy in atom–molecule collisions through quantum scattering resonances

Anisotropy is a fundamental property of particle interactions. It occupies a central role in cold and ultra-cold molecular processes, where long range forces have been found to significantly depend on orientation in ultra-cold polar molecule collisions. Recent experiments have demonstrated the emergence of quantum phenomena such as scattering resonances in the cold collisions regime due to quantization of the intermolecular degrees of freedom. Although these states have been shown to be sensitive to interaction details, the effect of anisotropy on quantum resonances has eluded experimental observation so far. Here, we directly measure the anisotropy in atom-molecule interactions via quantum resonances by changing the quantum state of the internal molecular rotor. We observe that a quantum scattering resonance at a collision energy of $k_B$ x 270 mK appears in the Penning ionization of molecular hydrogen with metastable helium only if the molecule is rotationally excited. We use state of the art ab initio and multichannel quantum molecular dynamics calculations to show that the anisotropy contributes to the effective interaction only for $H_2$ molecules in the first excited rotational state, whereas rotationally ground state $H_2$ interacts purely isotropically with metastable helium. Control over the quantum state of the internal molecular rotation allows us to switch the anisotropy on or off and thus disentangle the isotropic and anisotropic parts of the interaction. These quantum phenomena provide a challenging benchmark for even the most advanced theoretical descriptions, highlighting the advantage of using cold collisions to advance the microscopic understanding of particle interactions.