Finite temperature effects on the X-ray absorption spectra of lithium compounds: First-principles interpretation of X-ray Raman measurements

被引:44
作者
Pascal, Tod A. [1 ]
Boesenberg, Ulrike [2 ]
Kostecki, Robert [2 ]
Richardson, Thomas J. [2 ]
Weng, Tsu-Chien [3 ]
Sokaras, Dimosthenis [3 ]
Nordlund, Dennis [3 ]
McDermott, Eamon [4 ]
Moewes, Alexander [4 ]
Cabana, Jordi [2 ,5 ]
Prendergast, David [1 ]
机构
[1] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Mol Foundry, Div Mat Sci, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Environm Energy Technol Div, Berkeley, CA 94720 USA
[3] SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Stanford, CA 94720 USA
[4] Univ Saskatchewan, Dept Phys & Engn Phys, Saskatoon, SK S7N 5E2, Canada
[5] Univ Illinois, Dept Chem, Chicago, IL 60605 USA
关键词
SOLID-ELECTROLYTE INTERPHASE; LI-ION BATTERIES; ALKALI-HALIDE CRYSTALS; HYDROGEN STORAGE; FINE-STRUCTURE; K-EDGE; SCATTERING; SPECTROSCOPY; PSEUDOPOTENTIALS; MODEL;
D O I
10.1063/1.4856835
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. (C) 2014 AIP Publishing LLC.
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页数:13
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