Nonadiabatic Quantum Molecular Dynamics Simulations Research Articles

Catalysis in Extreme Field Environments: A Case Study of Strongly Ionized SiO2 Nanoparticle Surfaces.

High electric fields can significantly alter catalytic environments and the resultant chemical processes. Such fields arise naturally in biological systems but can also be artificially induced through localized nanoscale excitations. Recently, strong field excitation of dielectric nanoparticles has emerged as an avenue for studying catalysis in highly ionized environments, producing extreme electric fields. While the dynamics of laser-driven surface ion emission has been extensively explored, understanding the molecular dynamics leading to fragmentation has remained elusive. Here, we employ a multiscale approach performing nonadiabatic quantum molecular dynamics (NAQMD) simulations on hydrogenated silica surfaces in both bare and wetted environments under field conditions mimicking those of an ionized nanoparticle. Our findings indicate that hole localization drives fragmentation dynamics, leading to surface silanol dissociation within 50 fs and charge transfer-induced water splitting in wetted environments within 150 fs. Further insight into such ultrafast mechanisms is critical for the advancement of catalysis on the surface of charged nanosystems.

Photoinduced Negative Differential Resistance at a Graphene/Silicon Interface: A Nonadiabatic Quantum Molecular Dynamics Study.

The oscillatory retinal neuron (ORN) is a promising technology for achieving in-sensor cognitive image computing without external power. While its operation is based on photoinduced negative differential resistance (NDR) at a graphene/silicon interface to directly convert the incident optical signal into voltage oscillations, the optoelectronic mechanism of the NDR remains elusive. Here, nonadiabatic quantum molecular dynamics simulations show that the interplay of band alignment and charge transfer rates of photoexcited carriers at varying applied voltages gives rise to NDR at a graphene/silicon interface under illumination. Such intrinsic NDR at an interface, along with extrinsic circuit-level factors, could enable the much needed rational design of desired image computing functionality of ORN devices in the era of ubiquitous AI on edge devices.

Deep Well Trapping of Hot Carriers in a Hexagonal Boron Nitride Coating of Polymer Dielectrics.

Polymer dielectrics can be cost-effective alternatives to conventional inorganic dielectric materials, but their practical application is critically hindered by their breakdown under high electric fields driven by excited hot charge carriers. Using a joint experiment-simulation approach, we show that a 2D nanocoating of hexagonal boron nitride (hBN) mitigates the damage done by hot carriers, thereby increasing the breakdown strength. Surface potential decay and dielectric breakdown measurements of hBN-coated Kapton show the carrier-trapping effect in the hBN nanocoating, which leads to an increased breakdown strength. Nonadiabatic quantum molecular dynamics simulations demonstrate that hBN layers at the polymer-electrode interfaces can trap hot carriers, elucidating the observed increase in the breakdown field. The trapping of hot carriers is due to a deep potential well formed in the hBN layers at the polymer-electrode interface. Searching for materials with similar deep well potential profiles could lead to a computationally efficient way to design good polymer coatings that can mitigate breakdown.

Photoexcitation Induced Ultrafast Nonthermal Amorphization in Sb2Te3

Phase-change materials are of great interest for low-power high-throughput storage devices in next-generation neuromorphic computing technologies. Their operation is based on the contrasting properties of their amorphous and crystalline phases, which can be switched on the nanosecond time scale. Among the archetypal phase change materials based on Ge-Sb-Te alloys, Sb2Te3 displays a fast and energy-efficient crystallization-amorphization cycle due to its growth-dominated crystallization and low melting point. This growth-dominated crystallization contrasts with the nucleation-dominated crystallization of Ge2Sb2Te5. Here, we show that the energy required for and the time associated with the amorphization process can be further reduced by using a photoexcitation-based nonthermal path. We employ nonadiabatic quantum molecular dynamics simulations to investigate the time evolution of Sb2Te3 with 2.6, 5.2, 7.5, 10.3, and 12.5% photoexcited valence electron-hole carriers. Results reveal that the degree of amorphization increases with excitation, saturating at 10.3% excitation. The rapid amorphization originates from an instantaneous charge transfer from Te-p orbitals to Sb-p orbitals upon photoexcitation. Subsequent evolution of the excited state, within the picosecond time scale, indicates an Sb-Te bonding to antibonding transition. Concurrently, Sb-Sb and Te-Te antibonding decreases, leading to formation of wrong bonds. For photoexcitation of 7.5% valence electrons or larger, the electronic changes destabilize the crystal structure, leading to large atomic diffusion and irreversible loss of long-range order. These results highlight an ultrafast energy-efficient amorphization pathway that could be used to enhance the performance of phase change material-based optoelectronic devices.

An ab initio exciton model for singlet fission.

We present an ab initio exciton model that extends the Frenkel exciton model and includes valence, charge-transfer, and multiexcitonic excited states. It serves as a general, parameter-free, yet computationally efficient and scalable approach for simulation of singlet fission processes in multichromophoric systems. A comparison with multiconfigurational methods confirms that our exciton model predicts consistent energies and couplings for the pentacene dimer and captures the correct physics. Calculations of larger pentacene clusters demonstrate the computational scalability of the exciton model and suggest that the mixing between local and charge-transfer excitations narrows the gap between singlet and multiexcitonic states. Local vibrations of pentacene molecules are found to facilitate singlet-multiexcitonic state-crossing and hence are important for understanding singlet fission. The exciton model developed in this work also sets the stage for further implementation of the nuclear gradients and nonadiabatic couplings needed for first principles nonadiabatic quantum molecular dynamics simulations of singlet fission.

Differences in Sb2Te3 growth by pulsed laser and sputter deposition

High quality van der Waals chalcogenides are important for phase change data storage, thermoelectrics, and spintronics. Using a combination of statistical design of experiments and density functional theory, we clarify how out-of-equilibrium van der Waals epitaxial deposition methods can improve the crystal quality of Sb2Te3 films. We compare films grown by radio frequency sputtering and pulsed laser deposition (PLD). The growth factors that influence the crystal quality for each method are different. For PLD grown films a thin amorphous Sb2Te3 seed layer most significantly influences the crystal quality. In contrast, the crystalline quality of films grown by sputtering is rather sensitive to the deposition temperature and less affected by the presence of a seed layer. This difference is somewhat surprising as both methods are out-of-thermal-equilibrium plasma-based methods. Non-adiabatic quantum molecular dynamics simulations show that this difference originates from the density of excited atoms in the plasma. The PLD plasma is more intense and with higher energy than that used in sputtering, and this increases the electronic temperature of the deposited atoms, which concomitantly increases the adatom diffusion lengths in PLD. In contrast, the adatom diffusivity is dominated by the thermal temperature for sputter grown films. These results explain the wide range of Sb2Te3 and superlattice crystal qualities observed in the literature. These results indicate that, contrary to popular belief, plasma-based deposition methods are suitable for growing high quality crystalline chalcogenides.

Nonadiabatic molecular dynamics simulation of in a strong laser field**Xi Zhao was supported by Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-FG02-86ER13491), the National Natural Science Foundation of China (Grant No. 11904192); Ji-Gen Chen was supported by the National Natural Science Foundation of China (Grant No. 11975012);

We investigate the alignment dependence of the strong laser dissociation dynamics of molecule in the frame of real-time and real-space time-dependent density function theory coupled with nonadiabatic quantum molecular dynamics (TDDFT-MD) simulation. This work is based on a recent experiment study “ultrafast electron diffraction imaging of bond breaking in di-ionized acetylene” [Wolter et al, Science 354, 308–312 (2016)]. Our simulations are in excellent agreement with the experimental data and the analysis confirms that the alignment dependence of the proton dissociation dynamics comes from the electron response of the driving laser pulse. Our results validate the ability of the TDDFT-MD method to reveal the underlying mechanism of experimentally observed and control molecular dissociation dynamics.

PySpawn: Software for Nonadiabatic Quantum Molecular Dynamics.

The ab initio multiple spawning (AIMS) method enables nonadiabatic quantum molecular dynamics simulations in an arbitrary number of dimensions, with potential energy surfaces provided by electronic structure calculations performed on-the-fly. However, the intricacy of the AIMS algorithm complicates software development, deployment on modern shared computer resources, and postsimulation data analysis. PySpawn is a nonadiabatic molecular dynamics software package that addresses these issues. The program is designed to be easily interfaced with electronic structure software, and an interface to the TeraChem software package is described here. PySpawn introduces a task-based reorganization of the AIMS algorithm, allowing fine-grained restart capability and setting the stage for efficient parallelization in a future release. PySpawn includes a user-friendly and interactive Python analysis module that will enable novice users to painlessly adopt AIMS. As a demonstration of PySpawn's simulation capability and analysis module, we report complete active space self-consistent field-based AIMS simulations of the 1,2-dithienyl-1,2-dicyanoethene molecule, a promising molecular photoswitch.

Field-Induced Carrier Localization Transition in Dielectric Polymers.

Organic polymers offer many advantages as dielectric materials over their inorganic counterparts because of high flexibility and cost-effective processing, but their application is severely limited by breakdown in the presence of high electric fields. Dielectric breakdown is commonly understood as the result of avalanche processes such as carrier multiplication and defect generation that are triggered by field-accelerated hot carriers (electrons or holes). In stark contrast to inorganic dielectric materials, however, there remains no mechanistic understanding to enable quantitative prediction of the breakdown field in polymers. Here, we perform systematic study of different electric fields on hot carrier dynamics and resulting chemical damage in a slab of archetypal polymer, polyethylene, using nonadiabatic quantum molecular dynamics simulations. We found that high electric fields induce localized electronic states at the slab surface, with a critical transition occurring near the experimentally reported intrinsic breakdown field. This transition in turn facilitates strong polaronic coupling between charge carriers and atoms, which is manifested by severe damping of the time evolution of localized states and the presence of C-H vibrational resonance in the hot-carrier motion leading to rapid carbon-carbon bond breaking on the surface. Such polaronic localization transition may provide a critically missing prediction method for computationally screening dielectric polymers with high breakdown fields.

Hot-Carrier Dynamics and Chemistry in Dielectric Polymers.

Dielectric polymers are widely used in electronics and energy technologies, but their performance is severely limited by the electrical breakdown under a high electric field. Dielectric breakdown is commonly understood as an avalanche of processes such as carrier multiplication and defect generation that are triggered by field-accelerated hot electrons and holes. However, how these processes are initiated remains elusive. Here, nonadiabatic quantum molecular dynamics simulations reveal microscopic processes induced by hot electrons and holes in a slab of an archetypal dielectric polymer, polyethylene, under an electric field of 600 MV/m. We found that electronic-excitation energy is rapidly dissipated within tens of femtoseconds because of strong electron-phonon scattering, which is consistent with quantum-mechanical perturbation calculations. This in turn excites other electron-hole pairs to cause carrier multiplication. We also found that the key to chemical damage is localization of holes that travel to a slab surface and weaken carbon-carbon bonds on the surface. Such quantitative information can be incorporated into first-principles-informed, predictive modeling of dielectric breakdown.

Optical Control of Non-Equilibrium Phonon Dynamics.

The light-induced selective population of short-lived far-from-equilibrium vibration modes is a promising approach for controlling ultrafast and irreversible structural changes in functional nanomaterials. However, this requires a detailed understanding of the dynamics and evolution of these phonon modes and their coupling to the excited-state electronic structure. Here, we combine femtosecond mega-electronvolt electron diffraction experiments on a prototypical layered material, MoTe2, with non-adiabatic quantum molecular dynamics simulations and ab initio electronic structure calculations to show how non-radiative energy relaxation pathways for excited electrons can be tuned by controlling the optical excitation energy. We show how the dominant intravalley and intervalley scattering mechanisms for hot and band-edge electrons leads to markedly different transient phonon populations evident in electron diffraction patterns. This understanding of how tuning optical excitations affect phonon populations and atomic motion is critical for efficiently controlling light-induced structural transitions of optoelectronic devices.

Electronic Origin of Optically-Induced Sub-Picosecond Lattice Dynamics in MoSe2 Monolayer.

Atomically thin layers of transition metal dichalcogenide (TMDC) semiconductors exhibit outstanding electronic and optical properties, with numerous applications such as valleytronics. While unusually rapid and efficient transfer of photoexcitation energy to atomic vibrations was found in recent experiments, its electronic origin remains unknown. Here, we study the lattice dynamics induced by electronic excitation in a model TMDC monolayer, MoSe2, using nonadiabatic quantum molecular dynamics simulations. Simulation results show sub-picosecond disordering of the lattice upon photoexcitation, as measured by the Debye-Waller factor, as well as increasing disorder for higher densities of photogenerated electron-hole pairs. Detailed analysis shows that the rapid, photoinduced lattice dynamics are due to phonon-mode softening, which in turn arises from electronic Fermi surface nesting. Such mechanistic understanding can help guide optical control of material properties for functionalizing TMDC layers, enabling emerging applications such as phase change memories and neuromorphic computing.

Picosecond Electronic and Structural Dynamics in Photo-excited Monolayer MoSe2

Monolayers of semiconducting transitional metal dichalcogenides (TMDC) are emerging as strong candidate materials for next generation electronic and optoelectronic devices, with applications in field-effect transistors, valleytronics, and photovoltaics. Prior studies have demonstrated strong light-matter interactions in these materials, suggesting optical control of material properties as a promising route for their functionalization. However, the electronic and structural dynamics in response to electronic excitation have not yet been fully elucidated. In this work, we use non-adiabatic quantum molecular dynamics simulations based on time-dependent density functional theory to study lattice dynamics of a model TMDC monolayer of MoSe2 after electronic excitation. The simulation results show rapid, sub-picosecond lattice response, as well as finite-size effects. Understanding the sub-picosecond atomic dynamics is important for the realization of optical control of the material properties of monolayer TMDCs, which is a hopeful, straightforward tactic for functionalizing these materials.

Photo-induced Contraction of Layered Materials

ABSTRACTUltrafast atomic dynamics induced by electronic and optical excitation opens new possibilities for functionalization of two-dimensional and layered materials. Understanding the impact of perturbed valence band populations on both the strong covalent bonds and relatively weaker van der Waals interactions is important for these anisotropic systems. While the dynamics of strong covalent bonds has been explored both experimentally and theoretically, relatively fewer studies have focused on the impact of excitation on weak bonds like van der Waals and hydrogen-bond interactions. We perform non-adiabatic quantum molecular dynamics (NAQMD) simulations to study photo-induced dynamics in MoS2 bilayer. We observe photo-induced non-thermal contraction of the interlayer distance in the MoS2 bilayer within 100 femtoseconds after photoexcitation. We identify a large photo-induced redistribution of electronic charge density, whose Coulombic interactions could explain the observed inter-layer contraction.

Ultrafast non-radiative dynamics of atomically thin MoSe2

Photo-induced non-radiative energy dissipation is a potential pathway to induce structural-phase transitions in two-dimensional materials. For advancing this field, a quantitative understanding of real-time atomic motion and lattice temperature is required. However, this understanding has been incomplete due to a lack of suitable experimental techniques. Here, we use ultrafast electron diffraction to directly probe the subpicosecond conversion of photoenergy to lattice vibrations in a model bilayered semiconductor, molybdenum diselenide. We find that when creating a high charge carrier density, the energy is efficiently transferred to the lattice within one picosecond. First-principles nonadiabatic quantum molecular dynamics simulations reproduce the observed ultrafast increase in lattice temperature and the corresponding conversion of photoenergy to lattice vibrations. Nonadiabatic quantum simulations further suggest that a softening of vibrational modes in the excited state is involved in efficient and rapid energy transfer between the electronic system and the lattice.

Ultrafast X-ray Scattering from Molecules.

We present a theoretical framework for the analysis of ultrafast X-ray scattering experiments using nonadiabatic quantum molecular dynamics simulations of photochemical dynamics. A detailed simulation of a pump-probe experiment in ethylene is used to examine the sensitivity of the scattering signal to simulation parameters. The results are robust with respect to the number of wavepackets included in the total expansion of the molecular wave function. Overall, the calculated scattering signals correlate closely with the dynamics of the molecule.

The nature of free-carrier transport in organometal halide perovskites.

Organometal halide perovskites are attracting great attention as promising material for solar cells because of their high power conversion efficiency. The high performance has been attributed to the existence of free charge carriers and their large diffusion lengths, but the nature of carrier transport at the atomistic level remains elusive. Here, nonadiabatic quantum molecular dynamics simulations elucidate the mechanisms underlying the excellent free-carrier transport in CH3NH3PbI3. Pb and I sublattices act as disjunct pathways for rapid and balanced transport of photoexcited electrons and holes, respectively, while minimizing efficiency-degrading charge recombination. On the other hand, CH3NH3 sublattice quickly screens out electrostatic electron-hole attraction to generate free carriers within 1 ps. Together this nano-architecture lets photoexcited electrons and holes dissociate instantaneously and travel far away to be harvested before dissipated as heat. This work provides much needed structure-property relationships and time-resolved information that potentially lead to rational design of efficient solar cells.

Enhanced charge recombination due to surfaces and twin defects in GaAs nanostructures

Power conversion efficiency of gallium arsenide (GaAs) nanowire (NW) solar cells is severely limited by enhanced charge recombination (CR) at sidewall surfaces, but its atomistic mechanisms are not well understood. In addition, GaAs NWs usually contain a high density of twin defects that form a twin superlattice, but its effects on CR dynamics are largely unknown. Here, quantum molecular dynamics (QMD) simulations reveal the existence of an intrinsic type-II heterostructure at the (110) GaAs surface. Nonadiabatic quantum molecular dynamics (NAQMD) simulations show that the resulting staggered band alignment causes a photoexcited electron in the bulk to rapidly transfer to the surface. We have found orders-of-magnitude enhancement of the CR rate at the surface compared with the bulk value. Furthermore, QMD and NAQMD simulations show unique surface electronic states at alternating (111)A and (111)B sidewall surfaces of a twinned [111]-oriented GaAs NW, which act as effective CR centers. The calculated large surface recombination velocity quantitatively explains recent experimental observations and provides microscopic understanding of the underlying CR processes.

Twin superlattice-induced large surface recombination velocity in GaAs nanostructures

Semiconductor nanowires (NWs) often contain a high density of twin defects that form a twin superlattice, but its effects on electronic properties are largely unknown. Here, nonadiabatic quantum molecular dynamics simulation shows unique surface electronic states at alternating (111)A and (111)B sidewall surfaces of a twinned [111]-oriented GaAs NW, which act as effective charge-recombination centers. The calculated large surface recombination velocity quantitatively explains recent experimental observations and provides microscopic understanding of the underlying surface-recombination processes.

A divide-conquer-recombine algorithmic paradigm for large spatiotemporal quantum molecular dynamics simulations.

We introduce an extension of the divide-and-conquer (DC) algorithmic paradigm called divide-conquer-recombine (DCR) to perform large quantum molecular dynamics (QMD) simulations on massively parallel supercomputers, in which interatomic forces are computed quantum mechanically in the framework of density functional theory (DFT). In DCR, the DC phase constructs globally informed, overlapping local-domain solutions, which in the recombine phase are synthesized into a global solution encompassing large spatiotemporal scales. For the DC phase, we design a lean divide-and-conquer (LDC) DFT algorithm, which significantly reduces the prefactor of the O(N) computational cost for N electrons by applying a density-adaptive boundary condition at the peripheries of the DC domains. Our globally scalable and locally efficient solver is based on a hybrid real-reciprocal space approach that combines: (1) a highly scalable real-space multigrid to represent the global charge density; and (2) a numerically efficient plane-wave basis for local electronic wave functions and charge density within each domain. Hybrid space-band decomposition is used to implement the LDC-DFT algorithm on parallel computers. A benchmark test on an IBM Blue Gene/Q computer exhibits an isogranular parallel efficiency of 0.984 on 786 432 cores for a 50.3 × 10(6)-atom SiC system. As a test of production runs, LDC-DFT-based QMD simulation involving 16 661 atoms is performed on the Blue Gene/Q to study on-demand production of hydrogen gas from water using LiAl alloy particles. As an example of the recombine phase, LDC-DFT electronic structures are used as a basis set to describe global photoexcitation dynamics with nonadiabatic QMD (NAQMD) and kinetic Monte Carlo (KMC) methods. The NAQMD simulations are based on the linear response time-dependent density functional theory to describe electronic excited states and a surface-hopping approach to describe transitions between the excited states. A series of techniques are employed for efficiently calculating the long-range exact exchange correction and excited-state forces. The NAQMD trajectories are analyzed to extract the rates of various excitonic processes, which are then used in KMC simulation to study the dynamics of the global exciton flow network. This has allowed the study of large-scale photoexcitation dynamics in 6400-atom amorphous molecular solid, reaching the experimental time scales.