Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 7, Issue 10, Pages 3293-3303Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct200419x
Keywords
-
Funding
- NKBRSF [2011CB932400]
- NSFC of China [20933003, 11079006, 91026003]
- U.S. Department of Energy's Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory, Richland, WA
Ask authors/readers for more resources
The electronic absorption and emission spectra of free UO2Cl2 and its Ar-coordinated complexes below 27 000 cm(-1) are investigated at the levels of ab initio complete active space second-order perturbation theory (CASPT2) and coupled-cluster singles and doubles and perturbative triples [CCSD(T)] using valence 3 zeta-polarized basis sets. The influence of the argon matrix in the I2K experiment on the electronic spectra is explored by investigating the excited states of argon complexes ArnUO2Cl2. The calculated two most stable complexes with n = 2, 3 can explain the observed two matrix sites corresponding to the experimental two-component luminescence decay. In these uranyl complexes, Ar-coordination is found to have little influence on the (3)Phi (Omega = 2(g)) character of the luminescent state and on the electronic spectral shape. The calculations yield a coherent assignment of the experimental excitation spectra that improves on previous assignments. The simulated luminescence spectral curves based on the calculated spectral parameters of UO2Cl2 from both CASPT2 and CCSD(T) agree well with experiment.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available