期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c07572
关键词
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资金
- National Natural Science Foundation of China (NSFC) [22173060]
- NSFC International Excellent Young Science [22150610466]
- Ministry of Science and Technology of the People's Republic of China (MOST) National Foreign Experts Program [QN2021013001L]
- MOST Foreign Young Talents Program [WGXZ2022006L]
- NYU Shanghai Doctoral Fellowships
- NYU-ECNU Center for Computational Chemistry through a BOCO Postdoctoral Scholar award
- NYU Shanghai Boost Fund
This study used time-dependent density functional theory to simulate the X-ray absorption spectrum of the hydrated electron. A unique peak at 533 eV was observed, in agreement with recent experiments, and assigned to transitions from water O1s to the singly occupied molecular orbital (SOMO). The transitions acquired oscillator strength due to a mixing of a cavity-localized orbital and water antibonding orbitals.
The X-ray absorption spectrum (XAS) of the hydrated electron (e(aq)-) 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 O1s 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 4a1 and 2b2 antibonding orbitals. The mixing of antibonding orbitals has implications for the strength of couplings between e(aq)- and intramolecular modes of water.
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