Are High-Temperature Molten Salts Reactive with Excess Electrons? Case of ZnCl 2

Hung H. Nguyen; Vyacheslav S. Bryantsev; Claudio J. Margulis

doi:10.1021/acs.jpcb.3c04210

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Are High-Temperature Molten Salts Reactive with Excess Electrons? Case of ZnCl 2

Journal article

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Are High-Temperature Molten Salts Reactive with Excess Electrons? Case of ZnCl 2

Hung H. Nguyen, Vyacheslav S. Bryantsev and Claudio J. Margulis

The journal of physical chemistry. B, Vol.127(42), pp.9155-9164

09/27/2023

DOI: 10.1021/acs.jpcb.3c04210

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Abstract

New and exciting frontiers for the generation of safe and renewable energy have brought attention to molten inorganic salts of fluorides and chlorides. This is because high-temperature molten salts can act both as coolants and liquid fuel in next-generation nuclear reactors. Whereas research from a few decades ago suggests that salts are mostly unreactive to radiation, recent experiments hint at the fact that electrons generated in such extreme environments can react with the melt and form new species including nanoparticles. Our study probes the fate of an excess electron in molten ZnCl2 using first-principles molecular dynamics calculations. We find that on the time scale accessible to our study, an excess electron can be found in one of three states; the lowest-energy state can be characterized as a covalent Zn2Cl5•2– radical ion, the other two states are a solvated Zn•+ species (ZnCl3•2–) and a more delocalized species that still has some ZnCl3•2– character. Since for each of these, the singly occupied molecular orbital (SOMO) where the excess charge resides has a distinct and well-separated energy, the different species can in principle be characterized by their own electronic spectra. The study also sheds light onto what is commonly understood as the spectrum of a transient radical species which can be from the SOMO onto higher energy states or from the melt to pair with the excess electron leaving a hole in the liquid.

Electrical energy

Ions

Liquids

Metals

Salts

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Details

Title: Subtitle: Are High-Temperature Molten Salts Reactive with Excess Electrons? Case of ZnCl 2
Creators: Hung H. Nguyen - University of Iowa
Vyacheslav S. Bryantsev - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
Claudio J. Margulis - University of Iowa, Chemistry
Resource Type: Journal article
Publication Details: The journal of physical chemistry. B, Vol.127(42), pp.9155-9164
DOI: 10.1021/acs.jpcb.3c04210
ISSN: 1520-6106
eISSN: 1520-5207
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-AC02-05CH11231, DE-AC05-00OR22725, DE-SC0012704
Comment: Cover image: The Journal of Physical Chemistry B, Volume 127, Number 42
Language: English
Date published: 09/27/2023
Academic Unit: Chemistry
Record Identifier: 9984472857302771

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