Competing quantum tunneling processes of heavy and light particles in isocyanic acid radical anions

Jingjing Tang, Wenbin Fan, Lina Wang (), Xin Jiang, Beibei Sun, Yangyu Zhou, Wei Fang (), Xiaoqing Zeng and Mingfei Zhou ()
Additional contact information
Jingjing Tang: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Wenbin Fan: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Lina Wang: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Xin Jiang: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Beibei Sun: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Yangyu Zhou: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Wei Fang: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Xiaoqing Zeng: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Mingfei Zhou: Fudan University, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials

Nature Communications, 2025, vol. 16, issue 1, 1-8

Abstract: Abstract Quantum tunneling is known to be mass dependent. Here we report an unexpected mass effect on tunneling reactions in isocyanic acid radical anions (HNCO•−), which exhibit negative electron affinities. The cis- and trans-isomers of HNCO•− were generated in a solid neon matrix and their interconversion and electron-detachment tunneling kinetics were investigated using infrared absorption spectroscopy. The results reveal that electron tunneling, which involves some degree of nuclear motion of HNCO•− to neutral HNCO, occurs at a slower rate than the cis-to-trans isomerization of HNCO•−, with the latter following a distinct bond angle inversion pathway driven by the heavy carbon atom. This contrasts to the typical dominance of light hydrogen atom tunneling in cis-trans isomerization systems. These findings are rationalized by instanton theory calculations. Our model, which explicitly includes the neon matrix via a QM/MM approach, reveals that the carbon-driven pathway is favored by a lower barrier and shorter tunneling distance.

Date: 2025
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-025-65720-0 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-65720-0

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-025-65720-0

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().