期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 7, 期 10, 页码 3278-3292出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct200408j
关键词
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资金
- U.S. Department of Energy [DE-SC0001136]
- Computational Research (CCR) at the University at Buffalo
- U.S. Department of Energy's Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL)
- Department of Energy by the Battelle Memorial Institute [DE-AC06-76RLO-1830]
- DOE BES Heavy Element Chemistry Program
- U.S. Department of Energy, Office of Science, and NWChem development
Density functional theory (DFT) calculations of NMR chemical shifts and molecular g tensors with Gaussian-type orbitals are implemented via second-order energy derivatives within the scalar relativistic zeroth order regular approximation (ZORA) framework. Nonhybrid functionals, standard (global) hybrids, and range-separated (Coulomb-attenuated, long-range corrected) hybrid functionals are tested. Origin invariance of the results is ensured by use of gauge-including atomic orbital (GIAO) basis functions. The new implementation in the NWChem quantum chemistry package is verified by calculations of nuclear shielding constants for the heavy atoms in HX (X = F, Cl, Br, I, At) and H2X (X = O, S, Se, Te, Po) and Te-125 chemical shifts in a number of tellurium compounds. The basis set and functional dependence of g-shifts is investigated for 14 radicals with light and heavy atoms. The problem of accurately predicting F-19 NMR shielding in UF6-nCln, n = 1-6, is revisited. The results are sensitive to approximations in the density functionals, indicating a delicate balance of DFT self-interaction vs correlation. For the uranium halides, the range-separated functionals are not clearly superior to global hybrids.
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