TY  - JOUR
A1  - Eckert, Sebastian
A1  - Vaz da Cruz, Vinícius
A1  - Ochmann, Miguel
A1  - Ahnen, Inga von
A1  - Föhlisch, Alexander
A1  - Huse, Nils
T1  - Breaking the symmetry of pyrimidine
T2  - The journal of physical chemistry letters
N2  - 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 effective scattering duration through excitation energy detuning.
Y1  - 2021
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/63433
SN  - 1948-7185
VL  - 12
IS  - 35
SP  - 8637
EP  - 8643
PB  - American Chemical Society
CY  - Washington
ER  -