从水合电子的氧1s X射线吸收光谱看水反键轨道混合的证据。
Evidence for Water Antibonding Orbital Mixing in the Hydrated Electron from Its Oxygen 1s X-ray Absorption Spectrum.
作者信息
Li Xingpin, Jia Xiangyu, Paz Amiel S P, Cao Yuquan, Glover William J
机构信息
NYU Shanghai, 1555 Century Avenue, Shanghai, 200122, China.
NYU-ECNU Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshang Road, Shanghai, 200062, China.
出版信息
J Am Chem Soc. 2022 Nov 2;144(43):19668-19672. doi: 10.1021/jacs.2c07572. Epub 2022 Oct 17.
The X-ray absorption spectrum (XAS) of the hydrated electron () has been simulated using time-dependent density functional theory with a quantum mechanics/molecular mechanics description. A unique XAS peak at 533 eV is observed with an energy and intensity in quantitative agreement with recent time-resolved experiments, allowing its assignment as arising from water O1 transitions to the singly occupied molecular orbital (SOMO) in which the excess electron resides. The transitions acquire oscillator strength due to the SOMO comprising an admixture of a cavity-localized orbital and water 4 and 2 antibonding orbitals. The mixing of antibonding orbitals has implications for the strength of couplings between and intramolecular modes of water.
利用含时密度泛函理论并结合量子力学/分子力学描述，对水合电子（）的X射线吸收光谱（XAS）进行了模拟。在533 eV处观察到一个独特的XAS峰，其能量和强度与最近的时间分辨实验在定量上一致，从而可将其归因于水的O1跃迁到单占据分子轨道（SOMO），多余电子就位于该轨道中。由于SOMO由一个腔局域轨道与水的4和2反键轨道的混合组成，这些跃迁获得了振子强度。反键轨道的混合对水合电子与水分子内模式之间耦合的强度有影响。
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