1 research outputs found
Calculation of <sup>15</sup>N and <sup>31</sup>P NMR Chemical Shifts of Azoles, Phospholes, and Phosphazoles: A Gateway to Higher Accuracy at Less Computational Cost
A number
of computational schemes for the calculation of <sup>15</sup>N and <sup>31</sup>P NMR chemical shifts and shielding constants
in a series of azoles, phospholes, and phosphazoles was examined.
A very good correlation between calculated at the CCSDÂ(T) level and
experimental <sup>15</sup>N and <sup>31</sup>P NMR chemical shifts
was observed. It was found that basically solvent, vibrational, and
relativistic corrections are of the same order of magnitude and alternate
in sign, being, on average, of about 2–3 ppm in absolute value
but, being much larger (up to 14 ppm) in the case of solvent molecules
explicitly introduced into computational space. At the DFT level,
the performance of nine exchange–correlation functionals including
six conventional gradient functionals and three hybrid functionals
was studied. The most accurate results were reached with the OLYP
and Keal–Tozer’s family of functionals, KT1, KT2, and
KT3, while the most popular B3LYP and PBE0 functionals showed the
most unreliable results. On the basis of these data, we highly recommend
OLYP and KT2 functionals for the computation of <sup>15</sup>N and <sup>31</sup>P NMR chemical shifts at the DFT level in the diverse series
of nitrogen- and phosphorus-containing heterocycles. Benchmark calculations
of <sup>15</sup>N and <sup>31</sup>P NMR chemical shifts in a series
of larger nitrogen- and phosphorus-containing heterocycles were performed
at the DFT level in comparison with experiment and revealed the OLYP
functional in combination with the aug-pcS-3/aug-pcS-2 locally dense
basis set scheme as the most effective computational scheme