Simulating Cl K-edge X-ray absorption spectroscopy in MCl62- (M= U, Np, Pu) complexes and UOCl5- using time-dependent density functional theory

Journal Article · Fri Feb 21 00:00:00 EST 2014 · Theoretical Chemistry Accounts, 133(4):1-7

DOI:https://doi.org/10.1007/s00214-014-1463-z· OSTI ID:1126322

Govind, Niranjan; De Jong, Wibe A.

We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1126322
• Report Number(s): PNNL-SA-98444; 47703; KC0302030
• Journal Information: Theoretical Chemistry Accounts, 133(4):1-7, Journal Name: Theoretical Chemistry Accounts, 133(4):1-7
• Country of Publication: United States
• Language: English

Related Subjects

X-ray
absorption
spectroscopy
Time-Dependent Density Functional Theory
XANES
actinide
excitation
ab initio molecular dynamics
Environmental Molecular Sciences Laboratory