FCCC LOGO Faculty Publications
Sun Z , Zheng L , Chen M , Klein ML , Paesani F , Wu X
Electron-Hole Theory of the Effect of Quantum Nuclei on the X-Ray Absorption Spectra of Liquid Water
Phys Rev Lett. 2018 Sep 28;121(13) :137401
Back to previous list
Electron-hole excitation theory is used to unveil the role of nuclear quantum effects on the x-ray absorption spectral signatures of water, whose structure is computed via path-integral molecular dynamics with the MB-pol intermolecular potential model. Compared to spectra generated from the classically modeled water, quantum nuclei introduce important effects on the spectra in terms of both the energies and line shapes. Fluctuations due to delocalized protons influence the short-range ordering of the hydrogen bond network via changes in the intramolecular covalence, which broaden the preedge spectra. For intermediate-range and long-range ordering, quantum nuclei approach the neighboring oxygen atoms more closely than classical protons, promoting an "icelike" spectral feature with the intensities shifted from the main edge to the postedge. Computed spectra are in nearly quantitative agreement with the available experimental data.
1079-7114 Sun, Zhaoru Zheng, Lixin Chen, Mohan Klein, Michael L Paesani, Francesco Wu, Xifan Journal Article United States Phys Rev Lett. 2018 Sep 28;121(13):137401. doi: 10.1103/PhysRevLett.121.137401.