Probing the full cooperative structure of actinide chloride molten salts with Raman spectroscopy

Luke D. Gibson; Rajni Chahal; Raphael N. Ogbodo; Matthew S. Emerson; Markus Eisenbach; Ganesh Sivaraman; Santanu Roy; James F. Wishart; Claudio J. Margulis; Vyacheslav S. Bryantsev

doi:10.1038/s42004-026-02145-w

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Probing the full cooperative structure of actinide chloride molten salts with Raman spectroscopy

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Probing the full cooperative structure of actinide chloride molten salts with Raman spectroscopy

Luke D. Gibson, Rajni Chahal, Raphael N. Ogbodo, Matthew S. Emerson, Markus Eisenbach, Ganesh Sivaraman, Santanu Roy, James F. Wishart, Claudio J. Margulis and Vyacheslav S. Bryantsev

Communications chemistry

09/15/2026

DOI: 10.1038/s42004-026-02145-w

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Abstract

Understanding the structure of molten actinide chlorides is essential for advancing modern molten salt reactors, but scattering experiments on these are extremely challenging and therefore almost nonexistent, while Raman spectra are not straightforward to interpret for systems with significant collective structure. As a result, allegedly predictive simulations of actinide melts are rarely validated against experimental structural information; hence these predictions can differ significantly. Here, we combine density functional theory-based ab initio molecular dynamics simulations accelerated to nanosecond timescales with machine learning force fields, Raman spectral modeling, and analysis of projected vibrational densities of states to assign spectral features and directly link them to liquid structure in molten ThCl 4 . We find that the melt forms a percolating Th–Cl network dominated by sevenfold coordination, with terminal Th–Cl vibrations generating the ~340 cm⁻¹ Raman band and edge- and face-sharing linkages producing the 250–300 cm⁻¹ shoulder. Quantitative agreement with experiment requires explicit semicore treatment (68 e effective core potential (ECP) with 5 d 10 retained) and dispersion corrections, whereas large-core ECPs systematically red-shift the spectrum. This validated protocol establishes Raman measurements coupled with first-principles simulations as a quantitative structural benchmark for more accurate modeling of chloride melts containing major and minor actinides when no scattering data are available.

Details

Title: Subtitle: Probing the full cooperative structure of actinide chloride molten salts with Raman spectroscopy
Creators: Luke D. Gibson - Oak Ridge National Laboratory
Rajni Chahal - Oak Ridge National Laboratory
Raphael N. Ogbodo - University of Iowa
Matthew S. Emerson - Brookhaven National Laboratory
Markus Eisenbach - Oak Ridge National Laboratory
Ganesh Sivaraman - University at Buffalo, State University of New York
Santanu Roy - Oak Ridge National Laboratory
James F. Wishart - Brookhaven National Laboratory
Claudio J. Margulis - University of Iowa
Vyacheslav S. Bryantsev - Oak Ridge National Laboratory
Resource Type: Journal article
Publication Details: Communications chemistry
DOI: 10.1038/s42004-026-02145-w
ISSN: 2399-3669
eISSN: 2399-3669
Publisher: Springer Nature
Language: English
Electronic publication date: 09/15/2026
Academic Unit: Chemistry
Record Identifier: 9985230922902771

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