Abstract
AbstractEnergy, structure, and charge are fundamental quantities characterizing a molecule. Whereas the energy flow and structure change in chemical reactions are experimentally characterized, determining the atomic charges of a molecule in solution has been elusive, even for a triatomic molecule such as triiodide ion, I3−. Moreover, it remains to be answered how the charge distribution is coupled to the molecular geometry; which I-I bond, if two I-I bonds are unequal, dissociates depending on the electronic state. Here, femtosecond anisotropic x-ray solution scattering allows us to provide the following answers in addition to the overall rich structural dynamics. The analysis unravels that the negative charge of I3− is highly localized on the terminal iodine atom forming the longer bond with the central iodine atom, and the shorter I-I bond dissociates in the excited state, whereas the longer one in the ground state. We anticipate that this work may open a new avenue for studying the atomic charge distribution of molecules in solution and taking advantage of orientational information in anisotropic scattering data for solution-phase structural dynamics.
Funder
Institute of Basic Science; of South Korea. The grant Reference number is ;IBS-R033
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry,Multidisciplinary
Reference60 articles.
1. Bressler, C. et al. Femtosecond XANES study of the light-induced spin crossover dynamics in an iron(II) complex. Science 323, 489–492 (2009).
2. Vorobyev, V., Budkina, D. S. & Tarnovsky, A. N. Femtosecond excited-state dynamics and nitric oxide photorelease in a prototypical ruthenium nitrosyl complex. J. Phys. Chem. 11, 4639–4643 (2020).
3. Miller, N. A. et al. Polarized XANES monitors femtosecond structural evolution of photoexcited vitamin B12. J. Am. Chem. Soc. 139, 1894–1899 (2017).
4. Cordones, A. A. et al. Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex. Nat. Commun. 9, 1989 (2018).
5. Yoon, S.-J. et al. Multistimuli two-color luminescence switching via different slip-stacking of highly fluorescent molecular sheets. J. Am. Chem. Soc. 132, 13675–13683 (2010).
Cited by
8 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献