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Willard, Adam P.

Publications and source records attributed to Willard, Adam P..

10 records
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DOE OSTI2024

A theory of phonon-induced friction on molecular adsorbates

In this manuscript, we provide a general theory for how surface phonons couple to molecular adsorbates. Our theory maps the extended dynamics of a surface’s atomic vibrational motions to a generalized Langevin equation, and by doing so captures these dynamics in a single quantity: the non-Markovian friction. The different frequency components of this friction are the phonon modes of the surface slab weighted by their coupling to the adsorbate degrees of freedom. Using this formalism, we demonstrate that physisorbed species couple primarily to acoustic phonons while chemisorbed species couple to dispersionless local vibrations. We subsequently derive equations for phonon-adjusted reaction rates using transition state theory and demonstrate that these corrections improve agreement with experimental results for CO desorption rates from Pt(111).

Science & Technology - Other Topics↗
DOE OSTI2024

Persistent enhancement of exciton diffusivity in CsPbBr 3 nanocrystal solids

In semiconductors, exciton or charge carrier diffusivity is typically described as an inherent material property. Here, we show that the transport of excitons among CsPbBr 3 perovskite nanocrystals (NCs) depends markedly on how recently those NCs were occupied by a previous exciton. Using transient photoluminescence microscopy, we observe a striking dependence of the apparent exciton diffusivity on excitation laser power that does not arise from nonlinear exciton-exciton interactions or thermal heating. We interpret our observations with a model in which excitons cause NCs to transition to a long-lived metastable configuration that markedly increases exciton transport. The exciton diffusivity observed here (>0.15 square centimeters per second) is considerably higher than that observed in other NC systems, revealing unusually strong excitonic coupling between NCs. The finding of a persistent enhancement in excitonic coupling may help explain other photophysical behaviors observed in CsPbBr 3 NCs, such as superfluorescence, and inform the design of optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Trajectory Ensemble Methods Provide Single-Molecule Statistics for Quantum Dynamical Systems

The emergence of experiments capable of probing quantum dynamics at the single-molecule level requires the development of new theoretical tools capable of simulating and analyzing these dynamics beyond an ensemble-averaged description. In this article, we present an efficient method for sampling and simulating the dynamics of the individual quantum systems that make up an ensemble and apply it to study the nonequilibrium dynamics of the ubiquitous spin-boson model. We generate an ensemble of single-system trajectories, and we analyze this trajectory ensemble using tools from classical statistical mechanics. Our results demonstrate that the dynamics of quantum coherence is highly heterogeneous at the single-system level due to variations in the initial bath configuration, which significantly affects the transient exchange of coherence between the system and its bath. Here, we observe that single systems tend to retain coherence over time scales longer than that of the ensemble. We also compute a novel thermodynamic entanglement entropy that quantifies a thermodynamic driving force favoring system–bath entanglement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗