Simulating Cl K-edge X-ray absorption spectroscopy in MCl6 2− (M = U, Np, Pu) complexes and UOCl5 − using time-dependent density functional theory
- 302 Downloads
We report simulations of the X-ray absorption near edge structure at the Cl K-edge of actinide hexahalides MCl6 2− (M = U, Np, Pu) and the UOCl5 – complex using linear response time-dependent density functional theory extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl6 2− and PuCl6 2−. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics 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.
KeywordsActinides Plutonium Uranium Neptunium K-edge Chlorine X-ray absorption Spectroscopy XAS XANES
This research was funded by the BES Heavy Element Chemistry program in the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the US Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the Department of Energy by the Battelle Memorial Institute under Contract DE-AC06-76RLO-1830. Discussions with and access to unpublished UOCl5 structural data from Stosh Kozimor (LANL) are gratefully acknowledged.
- 1.Stöhr J (2003) NEXAFS spectroscopy. Springer, New York, pp 8–47Google Scholar
- 2.de Groot F, Kotani, A (2008) Core Level Spectroscopy of Solids. CRC Press, Boca Raton, FL:1–37, 457–462Google Scholar
- 3.Penfold T, Milne C, Chergui M (2013) Adv Chem Phys 153:1–41Google Scholar
- 23.Ikeno H, de Groot FMF, Stavitski E, Tanaka I (2009) J Phys: Condens Matter 21:104208Google Scholar
- 29.NWChem 6.3. http://www.nwchem-sw.org. Accessed 1 June 2013
- 36.Casida ME (1995) In: Chong PD (ed) Recent Advances in Density Functional Methods. World Scientific Publishing, River Edge, NJ, Vol. 1, Chap 5:155–192Google Scholar
- 37.Marques MA, Ullrich CA, Nogueira F, Rubio A, Burke K, Gross EK (eds) (2006) Time-dependent density functional theory (Lecture Notes in Physics), 1st edn. Springer, New YorkGoogle Scholar
- 57.Frenkel D, Smit B (2001) Understanding molecular simulation, 2nd edn: from algorithms to applications. Academic Press, San DiegoGoogle Scholar