Jan RR Verlet, Connor Jack Clarke, Eleanor Michi Burrow
{"title":"The valence electron affinity of uracil determined by anion cluster photoelectron spectroscopy","authors":"Jan RR Verlet, Connor Jack Clarke, Eleanor Michi Burrow","doi":"10.1039/d4cp02146k","DOIUrl":null,"url":null,"abstract":"The unoccupied π* orbitals of the nucleobases are considered to play important roles in low-energy electron attachment to DNA, inducing damage. While the lowest anionic state is unbound in all neutral nucleobases, it remains unclear even for the simplest nucleobase, uracil (U), whether its valence anion (U<small><sup>–</sup></small>) is adiabatically bound, which has important implications on the efficacy of damage processes. Using anion photoelectron spectroscopy, we demonstrate that the valence electron affinity (EAV) of U can be accurately measured within weakly solvating clusters, U<small><sup>–</sup></small>(Ar)<small><sub><em>n</em></sub></small> and U<small><sup>–</sup></small>(N<small><sub>2</sub></small>)<small><sub><em>n</em></sub></small>. Through extrapolation to the isolated U limit, we show that <em>EA</em><small><sub>V</sub></small> = −2 ± 18 meV. We discuss these findings in the context of electron attachment to U and its reorganization energy, and more generally establish guidance for the determination of molecular electron affinities from photoelectron spectroscopy of anion clusters.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp02146k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The unoccupied π* orbitals of the nucleobases are considered to play important roles in low-energy electron attachment to DNA, inducing damage. While the lowest anionic state is unbound in all neutral nucleobases, it remains unclear even for the simplest nucleobase, uracil (U), whether its valence anion (U–) is adiabatically bound, which has important implications on the efficacy of damage processes. Using anion photoelectron spectroscopy, we demonstrate that the valence electron affinity (EAV) of U can be accurately measured within weakly solvating clusters, U–(Ar)n and U–(N2)n. Through extrapolation to the isolated U limit, we show that EAV = −2 ± 18 meV. We discuss these findings in the context of electron attachment to U and its reorganization energy, and more generally establish guidance for the determination of molecular electron affinities from photoelectron spectroscopy of anion clusters.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
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