Journal of Physical Chemistry A, Vol.121, No.50, 9654-9662, 2017
NMR Chemical Shift of a Helium Atom as a Probe for Electronic Structure of FH, F-, (FHF)(-), and FH2+
In this work, we present the first results of outer electronic shell visualization by using a He-3 atom as a probe particle. As model objects we have chosen F-, FH, and FH2+ species, as well as the hydrogen-bonded complex H center dot center dot center dot F- at various H center dot center dot center dot F- distances (3.0, 2.5, 2.0, and 1.5 angstrom and equilibrium at ca. 1.14 angstrom). The interaction energy of investigated objects with helium atom (CCSD/aug-cc-pVTZ) and helium atom chemical shift (B3LYP/pcS-2) surfaces were calculated, and their topological analysis was performed. For comparison, the results of standard quantum mechanical approaches to electronic shell visualization were presented (ESP, ELF, ED, del(ED)-E-2). We show that the Laplacian of helium chemical shift, del(2)delta(He), is sensitive to fluorine atom lone pair localization regions, and it can be used for the visualization of the outer electronic shell, which could be used to evaluate the proton accepting ability. The sensitivity of del(2)delta(He) to lone pairs is preserved at distances as large as 2.0-2.5 angstrom from the fluorine nucleus (in comparison with the distance to ESP minima, located at 1.0-1.5 angstrom or maxima of ELF, which are as close as 0.6 angstrom to the fluorine nucleus).