Nonadiabatic Research Articles

Dual Passivation of Point Defects at Perovskite Grain Boundaries with Ammonium Salts Greatly Inhibits Nonradiative Charge Recombination.

Experiments demonstrate that grain boundaries (GBs) exhibit detrimental effect on carrier lifetimes in MAPbI3 (MA= CH3NH3+). On the basis of the nonadiabatic (NA) molecular dynamics simulations, we demonstrated that NH4Cl can simultaneously passivate the common point defects that introduce recombination centers at GBs and accelerate electron-hole recombination but shows small effects in the bulk. The MA interstitial (MAi) and the substitutional MA to Pb (MAPb) in pristine MAPbI3 leave the band gap and charge recombination rates largely unchanged but create deep electron traps at GBs by separately either distorting inorganic octahedra or creating an I-dimer. Cl- and NH4+ remove the in-gap states by either restoring the distorted octahedra or destroying the I-dimer. Thus, the band gap recovers to the pristine system, NA coupling decreases, and decoherence accelerates, extending the carrier lifetime even twice longer than MAPbI3. This study shows that the negative role of GBs can be removed by dually passivating with NH4Cl.

Interpolating Nonadiabatic Molecular Dynamics Hamiltonian with Inverse Fast Fourier Transform.

Nonadiabatic (NA) molecular dynamics (MD) allows one to investigate far-from-equilibrium processes in nanoscale and molecular materials at the atomistic level and in the time domain, mimicking time-resolved spectroscopic experiments. Ab initio NAMD is limited to about 100 atoms and a few picoseconds, due to computational cost of excitation energies and NA couplings. We develop a straightforward methodology that can extend ab initio quality NAMD to nanoseconds and thousands of atoms. The ab initio NAMD Hamiltonian is sampled and interpolated along a trajectory using a Fourier transform, and then, it is used to perform NAMD with known algorithms. The methodology relies on the classical path approximation, which holds for many materials and processes. To achieve a complete ab initio quality description, the trajectory can be obtained using an ab initio trained machine learning force field. The method is demonstrated with charge carrier trapping and relaxation in hybrid organic-inorganic and all-inorganic metal halide perovskites that exhibit complex dynamics and are actively studied for optoelectronic applications.

Charge-Compensated Doping Extends Carrier Lifetimes in SrTiO3 by Passivating Oxygen Vacancy Defects

Experiments reported that oxygen vacancies shorten the charge carrier lifetime of SrTiO3 but that it is greatly improved upon Al and Na doping. Using nonadiabatic (NA) molecular dynamics, we demonstrate that the in-gap hole trap state created by an oxygen vacancy can be eliminated by charge-compensated doping when two Ti4+ ions or two Sr2+ ions are equally replaced by Al3+ or Na+ ions. Nevertheless, Al3+ and Na+ reduce the strength of NA coupling to a different extent, resulting in increased charge carrier lifetimes of 4.6 and 1.3 ns. The lifetimes are several times longer than that of the pristine system and 3 orders of magnitude longer than that of defective SrTiO3, which is within 50 ps due to strong NA coupling. The weakly correlated electron and hole wave functions in doped systems accelerate decoherence, further delaying charge recombination. Our study rationalizes the complex charge-phonon dynamics in SrTiO3 and proposes charge-compensated doping for the design of advanced visible-light photocatalysts.

Significance of the Chemical Environment of an Element in Nonadiabatic Molecular Dynamics: Feature Selection and Dimensionality Reduction with Machine Learning.

Using supervised and unsupervised machine learning (ML) on features generated from nonadiabatic (NA) molecular dynamics (MD) trajectories under the classical path approximation, we demonstrate that mutual information with the NA Hamiltonian can be used for feature selection and model simplification. Focusing on CsPbI3, a popular metal halide perovskite, we observe that the chemical environment of a single element is sufficient for predicting the NA Hamiltonian. The conclusion applies even to Cs, although Cs does not contribute to the relevant wave functions. Interatomic distances between Cs and I or Pb and the octahedral tilt angle are the most important features. We reduce a typical 360-parameter ML force-field model to just a 12-parameter NA Hamiltonian model, while maintaining a high NA-MD simulation quality. Because NA-MD is a valuable tool for studying excited state processes, overcoming its high computational cost through simple ML models will streamline NA-MD simulations and expand the ranges of accessible system size and simulation time.

Density Functional Theory Half-Electron Self-Energy Correction for Fast and Accurate Nonadiabatic Molecular Dynamics.

The nonadiabatic (NA) process is crucial to photochemistry and photophysics and requires an atomistic understanding. However, conventional NA molecular dynamics (MD) for condensed-phase materials on the nanoscale are generally limited to the semilocal exchange-correlation functional, which suffers from the bandgap and thus NA coupling (NAC) problems. We consider TiO2 and a black phosphorus monolayer as two prototypical systems, perform NA-MD simulations of nonradiative electron-hole recombination, and demonstrate for the first time that density functional theory (DFT) half-electron self-energy correction can reproduce the bandgap, effective masses of carriers, luminescence line widths, NAC, and excited-state lifetimes of the two systems at the hybrid functional level while the computational cost remains at that of the Predew-Burke-Ernzerhof functional. Our study indicates that the DFT-1/2 method can greatly accelerate NA-MD simulations while maintaining the accuracy of the hybrid functional, providing an advantage for studying photoexcitation dynamics for large-scale condensed-phase materials.

Increasing Efficiency of Nonadiabatic Molecular Dynamics by Hamiltonian Interpolation with Kernel Ridge Regression

Nonadiabatic (NA) molecular dynamics (MD) goes beyond the adiabatic Born-Oppenheimer approximation to account for transitions between electronic states. Such processes are common in molecules and materials used in solar energy, optoelectronics, sensing, and many other fields. NA-MD simulations are much more expensive compared to adiabatic MD due to the need to compute excited state properties and NA couplings (NACs). Similarly, application of machine learning (ML) to NA-MD is more challenging compared with adiabatic MD. We develop an NA-MD simulation strategy in which an adiabatic MD trajectory, which can be generated with a ML force field, is used to sample excitation energies and NACs for a small fraction of geometries, while the properties for the remaining geometries are interpolated with kernel ridge regression (KRR). This ML strategy allows for one to perform NA-MD under the classical path approximation, increasing the computational efficiency by over an order of magnitude. Compared to neural networks, KRR requires little parameter tuning, saving efforts on model building. The developed strategy is demonstrated with two metal halide perovskites that exhibit complicated MD and are actively studied for various applications.

Benign Effects of Twin Boundaries on Charge Carrier Lifetime in Metal Halide Perovskites by a Time-Domain Study

Experiments show that two-dimensional twin boundaries (TBs) defects are benign to the excited-state lifetime of metal halide perovskites and solar cells performance. However, the mechanism remains unclear. By performing nonadiabatic (NA) molecular dynamics simulations on FAPbI3 (FA= HC(NH2)2+), we demonstrate that TBs increase the bandgap without introducing midgap states, promote charge separation by localizing electrons and holes that reduce NA coupling and accelerate the loss of coherence, slowing nonradiative electron-hole recombination by a factor of 2.3 compared to pristine FAPbI3, which occurs within sub-10 ns and agrees well with the experiment. Raising the temperature shortens the coherence time and reduces the NA coupling by increasing the charge localization due to the enhanced distortions of inorganic Pb-I lattice, making the recombination even slower. Our study rationalizes the positive influence of TBs and temperature on perovskite charge dynamics and emphasizes the roles played by the charge localization and quantum coherence.

Photoinduced Anomalous Electron Transfer Dynamics at a Lateral MoS2-Graphene Covalent Junction.

Photoinduced charge separation significantly affects the optoelectronic performance of the lateral MoS2-graphene junctions. Generally, an adiabatic mechanism governs electron transfer (ET) at a chemically binding interface. Counterintuitively, we demonstrate, using nonadiabatic (NA) molecular dynamics, that an NA mechanism dominates the ET from MoS2 to graphene in the lateral MoS2-graphene covalent junction. The anomalous ET mechanism arising from the built-in electric field formed at the interface that decreases the donor-acceptor interaction by driving electrons and holes moving to opposite directions. Driven by both graphene and MoS2 vibrations, the photoexcited electrons on MoS2 rapidly transfer into graphene by the NA mechanism within 200 fs, which is faster than electron-phonon energy relaxation and ensures that "hot" electrons can be successfully extracted before they cool and lose energy to heat. The study establishes a mechanistic understanding of the complex charge-phonon dynamics in the lateral MoS2-graphene junctions that are key to optoelectronic and photovoltaic applications.

Thermal-Driven Dynamic Shape Change of Bimetallic Nanoparticles Extends Hot Electron Lifetime of Pt/MoS2 Catalysts.

Using a combination of time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we demonstrate that the replacement of noble Pt with cheap Sn in the Pt nanoparticles sensitized MoS2 greatly retards the photoexcited "hot" electron relaxation. The simulations show that Sn substitution causes significant geometry distortion associated with the Sn dopant detaching from the Pt nanoparticle base, which decreases the NA coupling and creates an isolated trap state distant from the electron donor state. Generally, smaller NA coupling delays "hot" electron relaxation. At the same time, the photoexcited electron on MoS2 first populates the nanoparticles state and then slowly goes to the trap state, following relaxation to the nanoparticle acceptor state over 1 ps. As a result, the "hot" electron lives over 3.5 times longer than that in pristine Pt/MoS2 system. The long-lived "hot" electron associated with the reduced cost establishes a novel concept for developing high-efficient and cost-effective photocatalysts and photovoltaics.

Interpolating Nonadiabatic Molecular Dynamics Hamiltonian with Artificial Neural Networks.

Nonadiabatic (NA) molecular dynamics (MD) allows one to study far-from-equilibrium processes involving excited electronic states coupled to atomic motions. While NAMD involves expensive calculations of excitation energies and NA couplings (NACs), ground-state properties require much less effort and can be obtained with machine learning (ML) at a fraction of the ab initio cost. Application of ML to excited states and NACs is more challenging, due to costly reference methods, many states, and complex geometry dependence. We developed a NAMD methodology that avoids time extrapolation of excitation energies and NACs. Instead, under the classical path approximation that employs a precomputed ground-state trajectory, we use a small fraction (2%) of the geometries to train neural networks and obtain excited-state energies and NACs for the remaining 98% of the geometries by interpolation. Demonstrated with metal halide perovskites that exhibit complex MD, the method provides nearly two orders of computational savings while generating accurate NAMD results.

Nonadiabatic Kinetics in the Intermediate Coupling Regime: Comparing Molecular Dynamics to an Energy-Grained Master Equation.

We propose and test an extension of the energy-grained master equation (EGME) for treating nonadiabatic (NA) hopping between different potential energy surfaces, which enables us to model the competition between stepwise collisional relaxation and kinetic processes which transfer population between different electronic states of the same spin symmetry. By incorporating Zhu-Nakamura theory into the EGME, we are able to treat NA passages beyond the simple Landau-Zener approximation, along with the corresponding treatments of zero-point energy and tunneling probability. To evaluate the performance of this NA-EGME approach, we carried out detailed studies of the UV photodynamics of the volatile organic compound C6-hydroperoxy aldehyde (C6-HPALD) using on-the-fly ab initio molecular dynamics and trajectory surface hopping. For this multichromophore molecule, we show that the EGME is able to capture important aspects of the dynamics, including kinetic timescales, and diabatic trapping. Such an approach provides a promising and efficient strategy for treating the long-time dynamics of photoexcited molecules in regimes which are difficult to capture using atomistic on-the-fly molecular dynamics.

Concentric Approximation for Fast and Accurate Numerical Evaluation of Nonadiabatic Coupling with Projector Augmented-Wave Pseudopotentials.

We develop an efficient and accurate method for numerical evaluation of nonadiabatic (NA) coupling in the Kohn-Sham representation with projector augmented-wave (PAW) pseudopotentials that are commonly used in electronic structure calculations on nanoscale, condensed matter, and molecular systems. Without additional cost, the method provides an order of magnitude improvement in accuracy compared to the current technique, while it is 3-4 orders of magnitude faster than the exact evaluation. Atomic displacements over typical time steps in molecular dynamics (MD) simulations are much smaller than the size of the PAW core region, and therefore, evaluation of the NA in the core is simplified. The accuracy is demonstrated with three condensed matter systems. The method is robust to variation in the MD time step. The accurate NA coupling evaluation also helps in maintaining phase-consistency of the NA coupling and identifying trivial crossings of adiabatic states. The approach stimulates NAMD applications to modeling of modern materials and processes.

Doping-Induced Charge Localization Suppresses Electron-Hole Recombination in Copper Zinc Tin Sulfide: Quantum Dynamics Combined with Deep Neural Networks Analysis.

Nonradiative electron-hole recombination constitutes a major route for charge and energy losses in copper zinc tin sulfide (CZTS) solar cells. Using a combination of nonadiabatic (NA) molecular dynamics and deep neural networks (DNN), we demonstrated that electron-hole recombination is notably retarded by doping with Ag and Ag+Cd. The replacement of lighter Cu and/or Zn with heavier Ag and/or Cd reduces the NA coupling by separating electron and hole wave functions. Such replacement suppresses atomic motions and makes the phonon modes move to low-frequency region, which reduces NA coupling further but inhibits decoherence. The small magnitudes of NA coupling beat the long coherence time, delaying the electron-hole recombination from the Ag+Cd-codoping to the Ag doping system compared with pristine CZTS. The NA couplings predicted by the DNN algorithm lead to the time scales in agreement with the direct simulations. The study provides a robust strategy to design high-performance CZTS solar cells.

Elucidating the Influence of Sulfur Vacancies on Nonradiative Recombination Dynamics in Cu2ZnSnS4 Solar Absorbers.

We report a time-domain ab initio simulation of charge carrier trapping and relaxation dynamics in pristine and defect-containing kesterite Cu2ZnSnS4 (CZTS) structures. Our simulations show that introduction of a neutral sulfur vacancy in the CZTS system leads to a decrease of the charge recombination rate by a factor of ∼4, and the doubly positively charged sulfur vacancy results in a minor decrease of carrier lifetime, as compared to the pristine CZTS system. The neutral sulfur vacancy weakens the nonadiabatic (NA) electron-phonon coupling by moderately localizing charge density and accelerates the pure dephasing process, extending charge carrier lifetime. Therefore, the neutral sulfur vacancy is electrically benign. The doubly positively charged sulfur vacancy introduces a subgap state which is hardly populated, and recombination of the electron and hole bypassing the trap state dominates. As a result, the recombination rate decreases in the doubly charged sulfur vacancy structure. The reported results identified the key role of the sulfur-related vacancy on charge carrier trapping and relaxation of CZTS materials, carrying important implications for further optimization of CZTS and other thin-film solar cell materials.

Isotopic Exchange Extends Charge Carrier Lifetime in Metal Lead Perovskites by Quantum Dynamics Simulations.

One may expect that isotopic exchange has no influence on charge carrier lifetime and perovskite solar cell performance because isotopic effects do not affect the fundamental electronic structure of materials. Experiments defy this expectation. By performing nonadiabatic (NA) molecular dynamics simulations, we demonstrate that hydrogen and deuterium exchange significantly enhances the excited-state lifetime and stability of CH3NH3PbI3. Replacing lighter hydrogen with heavier deuterium suppresses the collective motions of organic and inorganic components, thus enhancing lattice stiffness and decreasing the NA coupling. Isotopic exchange further reduces NA coupling by localizing electron wave functions for separation of electrons and holes, which beats the extended coherence time, slowing down nonradiative electron-hole recombination from CH3ND3PbI3 to CD3ND3PbI3 with respect to the pristine system. The unchanged fundamental electronic structure together with the prolonged carrier lifetime and enhanced stability rationalize the improvement of the deuterated CH3NH3PbI3 solar cells. Our work provides valuable insights into isotope effects for the design of high-performance perovskite photovoltaic and optoelectronic devices.

Charge localization induced by reorientation of FA cations greatly suppresses nonradiative electron-hole recombination in FAPbI3 perovskites: A time-domain Ab Initio study

Recent experiments report the rotation of FA (FA=HC[NH2]2+) cations significantly influence the excited-state lifetime of FAPbI3. However, the underlying mechanism remains unclear. Using ab initio nonadiabatic (NA) molecular dynamics combined with time-domain density functional simulations, we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions. Slow nuclear motions simultaneously increase the decoherence time, which is overcome by the reduced NA coupling, extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3, which occurs within sub-nanosecond and agrees with experiment. Our study established the mechanism for the experimentally reported prolonged excited-state lifetime, providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.

Ab initio quantum dynamics of charge carriers in graphitic carbon nitride nanosheets

Graphitic carbon nitride (g-C3N4), a metal-free and visible light responsive photocatalyst, has garnered much attention due to its wide range of applications. In order to elucidate the role of dimensionality on the properties of photo-generated charge carriers, we apply nonadiabatic (NA) molecular dynamics combined with time-domain density functional theory to investigate nonradiative relaxation of hot electrons and holes, and electron-hole recombination in monolayer and bulk g-C3N4. The nonradiative charge recombination occurs on a nanosecond timescale and is faster in bulk than the nanosheet, in agreement with the experiment. The difference arises due to the smaller energy gap and participation of additional vibrations in the bulk system. The long carrier lifetimes are favored by small NA coupling and rapid phonon-induced loss of quantum coherence between the excited and ground electronic states. Decoherence is fast because g-C3N4 is soft and undergoes large scale vibrations. The NA coupling is small since electrons and holes are localized on different atoms, and the electron-hole overlap is relatively small. Phonon-driven relaxation of hot electrons and holes takes 100-200 fs and is slightly slower at higher initial energies due to participation of fewer vibrational modes. This feature of two-dimensional g-C3N4 contrasts traditional three-dimensional semiconductors, which exhibit faster relaxation at higher energies due to larger density of states, and can be used to extract hot carriers to perform useful functions. The ab initio quantum dynamics simulations present a comprehensive picture of the photo-induced charge carrier dynamics in g-C3N4, guiding design of photovoltaic and photocatalytic devices.

Two-Dimensional Perovskite Capping Layer Simultaneously Improves the Charge Carriers' Lifetime and Stability of MAPbI3 Perovskite: A Time-Domain Ab Initio Study.

Two- (2D) and three-dimensional (3D) heterostructured perovskites show enhanced stability and an extended charge lifetime compared to those of the 3D component. The mystery remains unexplored for both phenomena in the class of the typical type-I heterojunction. By using time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics simulations for the MA3Bi2I9/MAPbI3 (MA = CH3NH3+) junction, we demonstrate that the formation of I-Pb chemical bonds at the junction suppresses the atomic motions. The inhibited charge recombination in the junction is ascribed to the increased band gap, reduced NA coupling, and shortened coherence time. By localizing the hole wave function, the NA coupling is decreased by about a factor of 1.4. The presence of multiple phonon modes, particularly the Bi-I vibrations, accelerates decoherence about twice as fast as that in the pristine MAPbI3. As a result, the 2D capping layer reduces the recombination in MAPbI3 by more than a factor of 2, decreasing charge and energy losses. The strategy can be applied to optimize the performance of other 2D/3D heterostructured perovskite solar cells.

The Interplay Between Lead Vacancy and Water Rationalizes the Puzzle of Charge Carrier Lifetimes in CH3NH3PbI3: Time‐Domain Ab Initio Analysis

AbstractThe perovskite CH3NH3PbI3 excited‐state lifetimes exhibit conflicting experimental results under humid environments. Using ab initio nonadiabatic (NA) molecular dynamics, we demonstrate that the interplay between lead vacancy and water can rationalize the puzzle. The lead vacancy reduces NA coupling by localizing holes, slowing electron–hole recombination. By creating a deep electron trap state, the coexistence of a neutral lead vacancy and water molecules enhances NA coupling, accelerating charge recombination by a factor of over 3. By eliminating the mid‐gap state by accepting two photoexcited electrons, the negatively charged lead vacancy interacting with water molecules increases the carrier lifetime over 2 times longer than in the pristine system. The simulations rationalize the positive and negative effects of water on the solar cell performance exposure to humidity.

The Interplay Between Lead Vacancy and Water Rationalizes the Puzzle of Charge Carrier Lifetimes in CH3 NH3 PbI3 : Time-Domain Ab Initio Analysis.

The perovskite CH3 NH3 PbI3 excited-state lifetimes exhibit conflicting experimental results under humid environments. Using ab initio nonadiabatic (NA) molecular dynamics, we demonstrate that the interplay between lead vacancy and water can rationalize the puzzle. The lead vacancy reduces NA coupling by localizing holes, slowing electron-hole recombination. By creating a deep electron trap state, the coexistence of a neutral lead vacancy and water molecules enhances NA coupling, accelerating charge recombination by a factor of over 3. By eliminating the mid-gap state by accepting two photoexcited electrons, the negatively charged lead vacancy interacting with water molecules increases the carrier lifetime over 2 times longer than in the pristine system. The simulations rationalize the positive and negative effects of water on the solar cell performance exposure to humidity.