Through-space spin-spin coupling constants involving fluorine:benchmarking DFT functionals

Through-space spin–spin coupling constants (SSCCs) involving fluorine are computed applying Density Functional Theory and compared with experimental data to benchmark the performance of various functionals. In addition to the most often analysed J(FF) constants, we consider examples of J(FN), J(FP), J(FC) and J(FSe) constants. Basis sets optimised for the study of SSCCs are applied and thus we find the choice of the functional to be more important than the choice of the basis set. Different performance of DFT functionals is observed for different SSCCs, with the hybrid DFT functionals generally superior for the through-space couplings. When all the SSCCs are considered, PBE0 appears to be the most robust functional.</p

Spin-rotation and NMR shielding constants in HCl

The spin-rotation and nuclear magnetic shielding constants are analysed for both nuclei in the HCl molecule. Nonrelativistic ab initio calculations at the CCSD(T) level of approximation show that it is essential to include relativistic effects to obtain spin-rotation constants consistent with accurate experimental data. Our best estimates for the spin-rotation constants of 1H35Cl are CCl =−53.914 kHz and CH = 42.672 kHz (for the lowest rovibrational level). For the chlorine shielding constant, the ab initio value computed including the relativistic corrections, σ(Cl) = 976.202 ppm, provides a new absolute shielding scale; for hydrogen we find σ(H) = 31.403 ppm (both at 300 K). Combining the theoretical results with our new gas-phase NMR experimental data allows us to improve the accuracy of the magnetic dipole moments of both chlorine isotopes. For the hydrogen shielding constant, including relativistic effects yields better agreement between experimental and computed values