arXiv subjects

David T. Limmer

Publications and source records attributed to David T. Limmer.

At least 55 records · Page 3Linked to original sources

arXiv2024

Variational time reversal for free energy estimation in nonequilibrium steady states

Studying the structure of systems in nonequilibrium steady states necessitates tools that quantify population shifts and associated deformations of equilibrium free energy landscapes under persistent currents. Within the framework of stochastic thermodynamics, we establish a variant of the Kawasaki-Crooks equality that relates nonequilibrium free energy corrections in overdamped Langevin systems to heat dissipation statistics along time-reversed relaxation trajectories computable with molecular simulation. Using stochastic control theory, we arrive at a general variational approach to evaluate the Kawasaki-Crooks equality, and use it to estimate distribution functions of order parameters in specific models of driven and active matter, attaining substantial improvement in accuracy over simple perturbative methods.

cond-mat.stat-mech↗

arXiv2024

Splitting probabilities as optimal controllers of rare reactive events

The committor constitutes the primary quantity of interest within chemical kinetics as it is understood to encode the ideal reaction coordinate for a rare reactive event. We show the generative utility of the committor, in that it can be used explicitly to produce a reactive trajectory ensemble that exhibits numerically exact statistics as that of the original transition path ensemble. This is done by relating a time-dependent analogue of the committor that solves a generalized bridge problem, to the splitting probability that solves a boundary value problem under a bistable assumption. By invoking stochastic optimal control and spectral theory, we derive a general form for the optimal controller of a bridge process that connects two metastable states expressed in terms of the splitting probability. This formalism offers an alternative perspective into the role of the committor and its gradients, in that they encode forcefields that guarantee reactivity, generating trajectories that are statistically identical to the way that a system would react autonomously.

cond-mat.stat-mech↗

arXiv2024

Coherent control from quantum committment probabilities

We introduce a general definition of a quantum committor in order to clarify reaction mechanisms and facilitate control in processes where coherent effects are important. With a quantum committor, we generalize the notion of a transition state to quantum superpositions and quantify the effect of interference on the progress of the reaction. The formalism is applicable to any linear quantum master equation supporting metastability for which absorbing boundary conditions designating the reactant and product states can be applied. We use this formalism to determine the dependence of the quantum transition state on coherences in a polaritonic system and optimize the initialization state of a conical intersection model to control reactive outcomes, achieving yields of the desired state approaching 100%. In addition to providing a practical tool, the quantum committor provides a conceptual framework for understanding reactions in cases when classical intuitions fail.

physics.chem-ph↗

arXiv2024

Unraveling the mechanisms of triplet state formation in a heavy-atom free photosensitizer

Triplet excited state generation plays a pivotal role in photosensitizers, however the reliance on transition metals and heavy atoms can limit the utility of these systems. In this study, we demonstrate that an interplay of competing quantum effects control the high triplet quantum yield in a prototypical boron dipyrromethene-anthracene (BD-An) donor-acceptor dyad photosensitizer, which is only captured by an accurate treatment of both inner and outer sphere reorganization energies. Our ab initio-derived model provides excellent agreement with experimentally measured spectra, triplet yields and excited state kinetic data, including the triplet lifetime. We find that rapid triplet state formation occurs primarily via high-energy triplet states through both spin-orbit coupled charge transfer and El-Sayed's rule breaking intersystem crossing, rather than direct spin-orbit coupled charge transfer to the lowest lying triplet state. Our calculations also reveal that competing effects of nuclear tunneling, electronic state recrossing, and electronic polarizability dictate the rate of non-productive ground state recombination. This study sheds light on the quantum effects driving efficient triplet formation in the BD-An system, and offers a promising simulation methodology for diverse photochemical systems.

physics.chem-ph↗

arXiv2024

Enhanced ClNO$_2$ formation at the interface of sea-salt aerosol

The reactive uptake of $\mathrm{N_2O_5}$ on sea-spray aerosol plays a key role in regulating NO$_\mathrm{x}$ concentration in the troposphere. Despite numerous field and laboratory studies, a microscopic understanding of its heterogeneous reactivity remains unclear. Here, we use molecular simulation and theory to elucidate the chlorination of $\mathrm{N_2O_5}$ to form ClNO$_2$, the primary reactive channel within sea-spray aerosol. We find the formation of ClNO$_2$ is markedly enhanced at the air-water interface due to the stabilization of the charge-delocalized transition state, as evident from the formulation of bimolecular rate theory in heterogeneous environments. We explore the consequences of the enhanced interfacial reactivity in the uptake of $\mathrm{N_2O_5}$ using numerical solutions of molecular reaction-diffusion equations as well as their analytical approximations. Our results suggest that the current interpretation of aerosol branching ratios needs to be revisited.

physics.chem-ph↗

arXiv2024

In situ X-ray scattering reveals coarsening rates of superlattices self-assembled from electrostatically stabilized metal nanocrystals depend non-monotonically on driving force

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with new functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time- and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases \textit{in situ} and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small angle X-ray scattering (SAXS). By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (sub-second) initial nucleation and growth kinetics, while coarsening at later times depends non-monotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

cond-mat.soft↗

arXiv2024

On the Statistical Mechanics of Mass Accommodation at Liquid-Vapor Interfaces

We propose a framework for describing the dynamics associated with the adsorption of small molecules to liquid-vapor interfaces, using an intermediate resolution between traditional continuum theories that are bereft of molecular detail and molecular dynamics simulations that are replete with them. In particular, we develop an effective single particle equation of motion capable of describing the physical processes that determine thermal and mass accommodation probabilities. The effective equation is parameterized with quantities that vary through space away from the liquid-vapor interface. Of particular importance in describing the early time dynamics is the spatially dependent friction, for which we propose a numerical scheme to evaluate from molecular simulation. Taken together with potentials of mean force computable with importance sampling methods, we illustrate how to compute the mass accommodation coefficient and residence time distribution. Throughout, we highlight the case of ozone adsorption in aqueous solutions and its dependence on electrolyte composition.

physics.chem-ph↗

arXiv2023

Kinetics of the xanthophyll cycle and its role in photoprotective memory and response

Efficiently balancing photochemistry and photoprotection is crucial for survival and productivity of photosynthetic organisms in the rapidly fluctuating light levels found in natural environments. The ability to respond quickly to sudden changes in light level is clearly advantageous. In the alga Nannochloropsis oceanica we observed an ability to respond rapidly to sudden increases in light level which occur soon after a previous high-light exposure. This ability implies a kind of memory. In this work, we explore the xanthophyll cycle in N. oceanica as a short-term photoprotective memory system. By combining snapshot fluorescence lifetime measurements with a biochemistry-based quantitative model, we show that short-term "memory" arises from the xanthophyll cycle. In addition, the model enables us to characterize the relative quenching abilities of the three xanthophyll cycle components. Given the ubiquity of the xanthophyll cycle in photosynthetic organisms the model described here will be of utility in improving our understanding of vascular plant and algal photoprotection with important implications for crop productivity.

physics.bio-ph↗

arXiv2023

Nonequilibrium design strategies for functional colloidal assemblies

We use a nonequilibrium variational principle to optimize the steady-state, shear-induced interconversion of self-assembled nanoclusters of DNA-coated colloids. Employing this principle within a stochastic optimization algorithm allows us to discover design strategies for functional materials. We find that far-from-equilibrium shear flow can significantly enhance the flux between specific colloidal states by decoupling trade-offs between stability and reactivity required by systems in equilibrium. For isolated nanoclusters, we find nonequilibrium strategies for amplifying transition rates by coupling a given reaction coordinate to the background shear flow. We also find that shear flow can be made to selectively break detailed balance and maximize probability currents by coupling orientational degrees of freedom to conformational transitions. For a microphase consisting of many nanoclusters, we study the flux of colloids hopping between clusters. We find that a shear flow can amplify the flux without a proportional compromise on the microphase structure. This approach provides a general means of uncovering design principles for nanoscale, autonomous, functional materials driven far from equilibrium.

cond-mat.soft↗

arXiv2023

On the mechanism of polaritonic rate suppression from quantum transition paths

Polariton chemistry holds promise for facilitating mode-selective chemical reactions, but the underlying mechanism behind the rate modifications observed under vibrational strong coupling is not well understood. Using the recently developed quantum transition path theory, we have uncovered a mechanism of resonant suppression of a thermal reaction rate in a simple model polaritonic system, consisting of a reactive mode in a bath confined to a lossless microcavity with a single photon mode. This mechanism was uncovered by resolving the quantum dynamical reactive pathways and identifying their rate limiting transitions. Upon inspecting the wavefunctions associated with the rate limiting transition, we observed the formation of a polariton and identified the concomitant rate suppression as due to hybridization between the reactive mode and the cavity mode, which inhibits bath-mediated tunneling during the reaction. The transition probabilities that define the quantum master equation can be directly translated into a visualisation of the corresponding polariton energy landscape. This landscape exhibits a double funnel structure, with a large barrier between the initial and final states. This mechanism of resonant rate suppression is found to be robust to model parameters and computational details, and thus expected to be general.

physics.chem-ph↗

arXiv2023

Biexcitons are bound in CsPbBr3 Perovskite Nanocrystals

We study the energetics of quasi-particle excitations in CsPbBr3 perovskite nanocrystals using path integral molecular dynamics simulations. Employing detailed molecular models, we elucidate the interplay of anharmonic lattice degrees of freedom, dielectric confinement, and electronic correlation on exciton and biexciton binding energies over a range of nanocrystal sizes. We find generally good agreement with some experimental observations on binding energies, and additionally explain the observed size dependent Stokes shift. The explicit model calculations are compared to simplified approximations to rationalize the lattice contributions to binding. We find that polaron formation significantly reduces exciton binding energies, whereas these effects are negligible for biexciton interactions. While experimentally, the binding energy of biexcitons is uncertain, based on our study we conclude that biexcitons are bound in CsPbBr3.

physics.chem-ph↗

arXiv2023

Variational deep learning of equilibrium transition path ensembles

We present a time dependent variational method to learn the mechanisms of equilibrium reactive processes and efficiently evaluate their rates within a transition path ensemble. This approach builds off variational path sampling methodology by approximating the time dependent commitment probability within a neural network ansatz. The reaction mechanisms inferred through this approach are elucidated by a novel decomposition of the rate in terms of the components of a stochastic path action conditioned on a transition. This decomposition affords an ability to resolve the typical contribution of each reactive mode and their couplings to the rare event. The associated rate evaluation is variational and systematically improvable through the development of a cumulant expansion. We demonstrate this method in both over- and under-damped stochastic equations of motion, in low-dimensional model systems and the isomerization of solvated alanine dipeptide. In all examples, we find that we can obtain quantitatively accurate estimates of the rates of the reactive events with minimal trajectory statistics, and gain unique insight into the transitions through the analysis of their commitment probability.

physics.chem-ph↗

arXiv2023

Emergent Kelvin waves in chiral active matter

The phenomenological equations of hydrodynamics describe emergent behavior in many body systems. Their forms and the associated phenomena are well established when the quiescent state of the system is one of thermodynamic equilibrium, yet away from equilibrium relatively little is firmly established. Here, we deduce directly from first principles the hydrodynamic equations for a system far from equilibrium, a chiral active fluid in which both parity and time-reversal symmetries are broken. With our theory, we rationalize the emergence of a spontaneous boundary current in the confined fluid, a feature forbidden at equilibrium, which allows us to extract estimates of transport coefficients that we favorably compare to forced flows. The hydrodynamic solution reveals that the boundary current is analogous to a quasigeostrophic coastal current, a well known phenomenon in oceanography. Such currents are conjugate to a class of chiral waves called Kelvin waves. Motivated by this analogy, we demonstrate that an acoustic chiral Kelvin wave mode also exists in confined chiral active matter in the absence of an imposed rotation, originating from the spontaneous emergence of a Coriolis-like parameter in the bound modes of a chiral fluid.

cond-mat.soft↗

arXiv2023

Molecular Insights into Chemical Reactions at Aqueous Aerosol Interfaces

Atmospheric aerosols facilitate reactions between ambient gases and dissolved species. Here, we review our efforts to interrogate the uptake of these gases and the mechanisms of their reactions both theoretically and experimentally. We highlight the fascinating behavior of $\mathrm{N}_2\mathrm{O}_5$ in solutions ranging from pure water to complex mixtures, chosen because its aerosol-mediated reactions significantly impact global ozone, hydroxyl, and methane concentrations. As a hydrophobic, weakly soluble, and highly reactive species, $\mathrm{N}_2\mathrm{O}_5$ is a sensitive probe of the chemical and physical properties of aerosol interfaces. We employ contemporary theory to disentangle the fate of $\mathrm{N}_2\mathrm{O}_5$ as it approaches pure and salty water, starting with adsorption and ending with hydrolysis to HNO$_3$, chlorination to $\mathrm{ClNO}_2$, or evaporation. Flow reactor and gas-liquid scattering experiments probe even greater complexity as added ions, organic molecules, and surfactants alter interfacial composition and reaction rates. Together, we reveal a new perspective on multiphase chemistry in the atmosphere.

physics.chem-ph↗

arXiv2023

Probing reaction channels via reinforcement learning

We propose a reinforcement learning based method to identify important configurations that connect reactant and product states along chemical reaction paths. By shooting multiple trajectories from these configurations, we can generate an ensemble of configurations that concentrate on the transition path ensemble. This configuration ensemble can be effectively employed in a neural network-based partial differential equation solver to obtain an approximation solution of a restricted Backward Kolmogorov equation, even when the dimension of the problem is very high. The resulting solution, known as the committor function, encodes mechanistic information for the reaction and can in turn be used to evaluate reaction rates.

physics.chem-ph↗

arXiv2023

Odd mobility of a passive tracer in a chiral active fluid

Chiral active fluids break both time-reversal and parity symmetry, leading to exotic transport phenomena unobservable in ordinary passive fluids. We develop a generalized Green-Kubo relation for the anomalous lift experienced by a passive tracer suspended in a two-dimensional chiral active fluid subjected to an applied force. This anomalous lift is characterized by a transport coefficient termed the odd mobility. We validate our generalized response theory using molecular dynamics simulations, and we show that the asymmetric tracer mobility may be understood mechanically in terms of asymmetric deformations of the tracer-fluid density distribution function. We show that the even and odd components of the mobility decay at different rates with tracer size, suggesting the possibility of size-based particle separation using a chiral active working fluid.

cond-mat.soft↗

arXiv2023

Spin selective charge recombination in chiral donor-bridge-acceptor triads

In this paper we outline a physically motivated framework for describing spin-selective recombination processes in chiral systems, from which we derive spin-selective reaction operators for recombination reactions of donor-bridge-acceptor molecules, where the electron transfer is mediated by chirality and spin-orbit coupling. In general the recombination process is selective only for spin-coherence between singlet and triplet states, and it is not in general selective for spin polarisation. We find that spin polarisation selectivity only arises in hopping mediated electron transfer. We describe how this effective spin-polarisation selectivity is a consequence of spin-polarisation generated transiently in the intermediate state. The recombination process also augments the coherent spin dynamics of the charge separated state, which is found to have a significant effect on recombination dynamics and to destroy any long-lived spin polarisation. Although we only consider a simple donor-bridge-acceptor system, the framework we present here can be straightforwardly extended to describe spin-selective recombination processes in more complex systems.

physics.chem-ph↗

arXiv2023

Size-dependent lattice symmetry breaking determines the exciton fine structure of perovskite nanocrystals

The ordering of optically bright and dark excitonic states in lead-halide perovskite nanocrystals has been a matter of some debate. It has been proposed that the unusually short radiative lifetimes in these materials is due to an optically bright excitonic ground state, a unique situation among all nanomaterials. This proposal was based on the influence of the Rashba effect driven by lattice-induced inversion symmetry breaking. Direct measurement of the excitonic emission under magnetic fields has shown the signature of a dark ground state, bringing the role of the Rashba effect into question. Here, we use a fully atomistic theory to model the exciton fine structure of perovskite nanocrystals accounting for the realistic lattice distortion at the nanoscale. We calculate optical gaps and exciton fine structure that compare favorably with a wide range of experimental works. We find a non-monotonic dependence of the exciton fine structure splittings due to a size dependence structural transition between cubic and orthorhombic phases. In addition, the excitonic ground state is found to be dark with nearly pure spin triplet character resulting from a small Rashba coupling. We additionally explore the intertwined effects of lattice distortion and nanocrystal shape on the fine structure splittings, clarifying observations on poly-disperse nanocrystals.

physics.chem-ph↗