Weinhardt Lothar, Hauschild Dirk, Steininger Ralph, Wansorra Constantin, Yang Wanli, Heske Clemens
Institute for Photon Science and Synchrotron Radiation (IPS), Karlsruhe Institute of Technology (KIT), Kaiserstrasse 12, 76131 Karlsruhe, Germany.
Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Kaiserstraasse 12, 76131 Karlsruhe, Germany.
J Phys Chem Lett. 2024 Oct 24;15(42):10576-10582. doi: 10.1021/acs.jpclett.4c02329. Epub 2024 Oct 14.
Dimethyl sulfoxide (DMSO) is an important polar solvent that derives its unique properties from the lone pair and the strong polar bond at the sulfinyl functional group. To derive the local and symmetry-resolved electronic structure of liquid DMSO, we have used resonant inelastic soft X-ray scattering (RIXS) maps at the S L, C K, and O K edges. The experimental data are compared to calculations of spectra based on density functional theory, which allows a detailed analysis of the molecular orbitals throughout the molecule. In the RIXS maps, we find the signature of molecular-field splitting of the S 2p core levels, vibronic coupling, and ultrafast nuclear dynamics on the time scale of the RIXS process.
二甲基亚砜（DMSO）是一种重要的极性溶剂，其独特性质源于亚磺酰官能团上的孤对电子和强极性键。为了获得液态二甲基亚砜的局域和对称性分辨电子结构，我们利用了在硫（S）L、碳（C）K和氧（O）K边的共振非弹性软X射线散射（RIXS）图谱。实验数据与基于密度泛函理论的光谱计算结果进行了比较，这使得我们能够对整个分子中的分子轨道进行详细分析。在RIXS图谱中，我们发现了硫2p芯能级的分子场分裂、振子耦合以及RIXS过程时间尺度上的超快核动力学的特征。
