Breaking the symmetry of pyrimidine
- Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effectiveSymmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning.…
Author details: | Sebastian EckertORCiDGND, Vinícius Vaz da CruzORCiD, Miguel OchmannORCiDGND, Inga von AhnenGND, Alexander FöhlischORCiDGND, Nils HuseORCiDGND |
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DOI: | https://doi.org/10.1021/acs.jpclett.1c01865 |
ISSN: | 1948-7185 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/34472857 |
Title of parent work (English): | The journal of physical chemistry letters |
Subtitle (English): | solvent effects and core-excited state dynamics |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Date of first publication: | 2021/09/02 |
Publication year: | 2021 |
Release date: | 2024/04/26 |
Volume: | 12 |
Issue: | 35 |
Number of pages: | 7 |
First page: | 8637 |
Last Page: | 8643 |
Funding institution: | ERC-ADG-2014 Advanced Investigator Grant under the Horizon 2020 EU [669531 EDAX]; Max Planck SocietyMax Planck SocietyFoundation CELLEX; City of Hamburg; German Science Foundation (DFG)German Research Foundation (DFG) [SFB 925] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
Peer review: | Referiert |
Publishing method: | Open Access / Hybrid Open-Access |
License (German): | CC-BY-NC-ND - Namensnennung, nicht kommerziell, keine Bearbeitungen 4.0 International |