Affiliation:
1. Department of Applied Physics , School of Physical Electronics, University of Electronic Science and Technology of China , Chengdu 610054 , P.R. China
Abstract
Abstract
Density functional theory (DFT) calculations of the structures and the Cu2+
g factors (g
x
, g
y
and g
z
) and hyperfine coupling tensor A (A
x
, A
y
and A
z
) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu–Cu distances were calculated and compared with the relevant systems.
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy,Mathematical Physics
Reference58 articles.
1. M. Daniel, R. M. Daniel, and V. Jaume, Chem. Soc. Rev. 36, 770 (2007).10.1039/b501600m
2. N. Klein, I. Denkovska, K. Gedrich, U. Stoeck, A. Henschel, et al., Angew. Chem. Int. Ed. 48, 1 (2009).10.1002/anie.200890275
3. A. C. McKinlay, R. E. Morris, P. Horcajada, G. Férey, R. Gref, et al., Angew. Chem. Int. Ed. 49, 6260 (2010).10.1002/anie.201000048
4. W. Xu and Y. Q. Zheng, J. Chem. Crystallogr. 42, 313 (2012).10.1007/s10870-011-0244-y
5. S. G. Baca, I. L. Malaestean, T. D. Keene, H. Adams, M. D. War, et al., Inorg. Chem. 47, 11108 (2008).10.1021/ic8014145
Cited by
8 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献