Real-Time KMC Simulation of Vacancy-Mediated Intermixing in Au@Ag Octahedral Core–Cubic Shell Nanocrystals with Ab Initio-Guided Kinetics

Han, Yong; Evans, James W.

doi:10.1021/acsnano.4c06435

Real-Time KMC Simulation of Vacancy-Mediated Intermixing in Au@Ag Octahedral Core–Cubic Shell Nanocrystals with Ab Initio-Guided Kinetics

Journal Article · Wed Jul 31 00:00:00 EDT 2024 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.4c06435· OSTI ID:2434277

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Ames Laboratory (AMES), Ames, IA (United States); Iowa State University, Ames, IA (United States)

Utilization of core–shell rather than monometallic nanocrystals (NCs) facilitates fine-tuning of NC properties for applications. However, compositional evolution via intermixing can degrade these properties prompting recent experimental studies. We develop an atomistic-level stochastic model for vacancy-mediated intermixing exploiting a formalism which allows incorporation at an ab initio density functional theory level of not just the thermodynamics of vacancy formation, but also relevant diffusion barriers for a vast number of possible local environments (in the core and in the shell, at the interface, and in the intermixed phase). This facilitates a predictive treatment and comprehensive understanding of intermixing on the relevant time scale (e.g., 10¹–10³ s). In contrast, previous modeling at the atomistic level utilized only unrealistic generic prescriptions of barriers or employed simplified continuum treatments. For Au@Ag octahedral core–cubic shell NCs, our modeling not only captures the experimentally observed rate or time scale for intermixing of ~100 s at 450 °C for 60 nm NCs, but also elucidates the underlying rate controlling processes and the effective intermixing barrier.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: NERSC; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; AC02-07CH11358

OSTI ID:: 2434277

Report Number(s):: IS-J--11,398

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 36 Vol. 18; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Au@Ag core−shell nanocrystal
KMC simulation
defects in solids
diffusion
energy
gold
interfaces
intermixing
realistic vacancy-mediated diffusion kinetics
stochastic modeling

Real-Time KMC Simulation of Vacancy-Mediated Intermixing in Au@Ag Octahedral Core–Cubic Shell Nanocrystals with Ab Initio-Guided Kinetics

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