The coupled transfer of electrons and protons is a central feature biological molecular catalysis, yet fundamental aspects these reactions remain poorly understood. In this study, we extend the ring polymer dynamics (RPMD) method to enable direct simulation proton-coupled electron (PCET) across wide range physically relevant regimes. system-bath model for symmetric, co-linear PCET in condensed phase, RPMD trajectories reveal distinct kinetic pathways associated with sequential concerted...

In this work, we derive a multi-fragment real-time extension of the projected density matrix embedding theory (pDMET) designed to treat non-equilibrium electron dynamics in strongly correlated systems. As previously developed static pDMET, real time pDMET partitions total system into many fragments; coupling between each fragment and rest is treated through compact representation environment terms quantum bath. The involves simultaneously propagating wavefunctions for separate fragment-bath...

Concerted proton-electron transfer (CPET) reactions in iron carboxy-tetraphenylporphyrin complexes have been investigated using both experimental and theoretical methods. Synthetic heme models abstract H+ e- from the hydroxylamine TEMPOH or an ascorbate derivative, kinetics of reaction indicate concerted e-. Phenylene linker domains vary electron donor/acceptor separation by approximately 4 Å. The rate data extensive molecular simulations show that electronic coupling decay constant (β)...

We use quantized molecular dynamics simulations to investigate the competition between concerted and sequential proton-coupled electron-transfer (PCET) reaction mechanisms in inorganic catalysts. By analyzing reactive nonadiabatic PCET trajectories computing both rate constants, we characterize various features that govern reactions, including solvent polarity, ligand-mediated electron–proton interactions, intrinsic proton-transfer (PT) energy barrier. Using atomistic with over 1200 atoms,...

Significance Protein fluctuations and hydrogen-bond networks play an important—although incompletely understood—role in facilitating efficient biological electron transfer (ET). Experimental mutagenesis results provide evidence for the role of protein motions Ru-modified azurin ET, a quintessential example ET. A recently developed nonadiabatic molecular dynamics method allows exploration nature fluctuations, providing insight into conformational that accompany ET azurin. In particular,...

We present a density-matrix embedding theory (DMET) study of the one-dimensional Hubbard-Holstein model, which is paradigmatic for interplay electron-electron and electron-phonon interactions. Analyzing single-particle excitation gap, we find direct Peierls insulator to Mott phase transition in adiabatic regime slow phonons contrast rather large intervening metallic anti-adiabatic fast phonons. benchmark DMET results both on-site energies gaps against renormalization group (DMRG) good...

We investigate the cluster size convergence of energy and observables using two forms density matrix embedding theory (DMET): original form (CDMET) a new formulation motivated by dynamical approximation (DCA-DMET). Both methods are applied to half-filled one- two-dimensional Hubbard models sign-problem free auxiliary-field quantum Monte Carlo (AFQMC) impurity solver, which allows for treatment large clusters up 100 sites. While CDMET is more accurate at smaller sizes, DCA- DMET exhibits...

We introduce real-time density matrix embedding theory (DMET), a dynamical quantum for computing non-equilibrium electron dynamics in strongly correlated systems. As the previously developed static DMET, DMET partitions system into an impurity corresponding to region of interest coupled surrounding environment, which is efficiently represented by bath same size as impurity. In this work, we focus on simplified single-impurity time-dependent formulation first step toward multi-impurity...

Preferred crystallographic orientation in polycrystalline films is desirable for efficient charge carrier transport metal halide perovskites and semiconductors. However, the mechanisms that determine preferred of are still not well understood. In this work, we investigate lead bromide perovskites. We show solvent precursor solution organic A-site cation strongly affect deposited perovskite thin films. Specifically, solvent, dimethylsulfoxide, influences early stages crystallization induces...

We investigate the performance of recently developed kinetically-constrained ring polymer molecular dynamics (KC-RPMD) method for description model condensed-phase electron transfer (ET) reactions in which solvent and donor–acceptor play an important role. Comparison KC-RPMD with results from Golden-Rule rate theories numerically exact quantum calculations demonstrates that accurately captures combination electronic- nuclear-dynamical effects throughout Marcus (intermediate friction) Zusman...

In this work, we investigate the capability of using real-time time-dependent density functional theory (RT-TDDFT) in conjunction with a complex absorbing potential (CAP) to simulate intermolecular Coulombic decay (ICD) processes following ionization an inner-valence electron. We examine ICD dynamics series noncovalent bonded dimer systems, including hydrogen-bonded and purely van der Waals (VdW)-bonded systems. comparison previous show that RT-TDDFT simulations CAP correctly capture...

Similar to graphene, diamane is a single layer of diamond that has been investigated in recent years due its peculiar mechanical, thermal, and electronic properties. Motivated by earlier work showed an exceptionally high intra-plane thermal conductivity diamane, this work, we investigate the interfacial resistance (R) between graphene using non-equilibrium classical molecular dynamics simulations. The calculated R for pristine AB-stacked at room temperature 1.89 × 10-7 K m2/W, which...

The O((3)P) + C(2)H(4) reaction provides a crucial, initial understanding of hydrocarbon combustion. In this work, the lowest-lying triplet potential energy surface is extensively explored at multiconfiguration self-consistent field (MCSCF) and MRMP2 levels with preliminary crossing investigation; in cases that additional dynamical correlation necessary, MR-AQCC stationary points are also determined. particular, careful determination active space along intrinsic pathway necessary; some...

We explore model electron dynamics of an atom scattering off a surface within the time-dependent complete active space self-consistent field (TD-CASSCF) approximation. focus especially on hydrogen and its resulting spin starting from initially spin-polarized state. Our results reveal competing electronic time scales that are governed by structure as well character atom. The nonadiabaticity reported final polarization scattered atom, which may be probed in future experiments.

We introduce real-time density matrix embedding theory (DMET), a dynamical quantum for computing non-equilibrium electron dynamics in strongly correlated systems. As the previously developed static DMET, DMET partitions system into an impurity corresponding to region of interest coupled surrounding environment, which is efficiently represented by bath same size as impurity. In this work, we focus on single-impurity time-dependent first step towards full multi-impurity theory. The equations...

In this work, we investigate the capability of using real-time time-dependent density functional theory (RT-TDDFT) in conjunction with a complex absorbing potential (CAP) to simulate intermolecular Coulombic decay (ICD) processes following ionization an innervalence electron. We examine ICD dynamics series non-covalent bonded dimer systems, including H2O-H2O, HF-HF, Ar-H2O, Ne-H2O and Ne-Ar. consider initial state generated from inner-valence excitation on either monomer within each dimer,...

The non-adiabatic ring polymer molecular dynamics (NRPMD) method, which combines the path-integral framework for nuclei with Meyer-Miller-Stock-Thoss mapping of electronic states, is a powerful tool simulating including nuclear quantum effects. However, challenges arise in utilizing NRPMD associated zero-point energy leakage between and degrees freedom ambiguities how to apply method under non-equilibrium conditions. Here, we explore several variants compare their performance using set...

The non-adiabatic ring polymer molecular dynamics (NRPMD) method, which combines the path-integral framework for nuclei with Meyer-Miller-Stock-Thoss mapping of electronic states, is a powerful tool simulating including nuclear quantum effects. However, challenges arise in utilizing NRPMD associated zero-point energy leakage between and degrees freedom ambiguities how to apply method under non-equilibrium conditions. Here, we explore several variants compare their performance using set...

Proton-coupled electron transfer (PCET) reactions are ubiquitous throughout chemistry and biology. However, challenges arise in both the experimental theoretical investigation of PCET reactions; rare-event nature coupling between quantum mechanical electron- proton-transfer with slower classical dynamics surrounding environment necessitates development robust simulation methodology. In following dissertation, novel path-integral based methods developed employed for direct reaction mechanisms...

We explore model electron dynamics of an atom scattering off a surface within the time-dependent complete active space self consistent field (TD-CASSCF) approximation. focus especially on hydrogen and its resulting spin-dynamics starting from initially spin-polarized state. Our results reveal competing electronic time-scales that are governed by structure as well character atom. The timescales nonadiabaticity reported final spin-polarization scattered atom, which may be probed in future experiments.