Research output: Contribution to journal › Article › peer-review
Outer Electronic Shell Visualization by NMR Chemical Shift Laplacian of a Helium Probe. / Tolstoy, Peter M.; Денисов, Глеб Семенович; Тупикина, Елена Юрьевна; Ефимова, Александра Александровна.
In: Journal of Computational Chemistry, Vol. 39, No. 29, 05.11.2018, p. 2459-2462.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Outer Electronic Shell Visualization by NMR Chemical Shift Laplacian of a Helium Probe
AU - Tolstoy, Peter M.
AU - Денисов, Глеб Семенович
AU - Тупикина, Елена Юрьевна
AU - Ефимова, Александра Александровна
N1 - Funding Information: [a] E. Yu. Tupikina, A. A. Efimova, G. S. Denisov Department of Physics, St. Petersburg State University, Uljanovskaja 1, St. Petersburg 198504, Russia [b] P. M. Tolstoy Center for Magnetic Resonance, St. Petersburg State University, Universitetsky pr. 26, 198504, Russia E-mail: peter.tolstoy@spbu.ru Contract Grant sponsor: Russian Foundation for Basic Research; Contract Grant number: 17-03-00497
PY - 2018/11/5
Y1 - 2018/11/5
N2 - A new method of visualization of lone pairs is proposed using fluorine atoms in fluoroacetylene, trifluoroethylene, and fluoroform (sp, sp 2, and sp 3 hybridized carbons) as an example. The space around fluorines was probed by a helium atom and at each point 3He NMR chemical shift δ He and its Laplacian ∇ 2δ He were calculated. The ∇ 2δ He isosurfaces have symmetrical toroidal shapes along CF axes; the maximum values of ∇ 2δ He are reached at about 1.5 Å from fluorine atom center in the direction roughly coinciding with the lone pair localization. The absolute values of the ∇ 2δ He could be used to quantify the electron-rich regions of lone pairs. The results are compared with more common visualization methods—3D maps of the molecular electrostatic potential and the electron localization function. We show that a helium atom could be used for evaluation of fine features of molecular electronic shell, since 3He NMR spectral characteristics remain sensitive at relatively large distances.
AB - A new method of visualization of lone pairs is proposed using fluorine atoms in fluoroacetylene, trifluoroethylene, and fluoroform (sp, sp 2, and sp 3 hybridized carbons) as an example. The space around fluorines was probed by a helium atom and at each point 3He NMR chemical shift δ He and its Laplacian ∇ 2δ He were calculated. The ∇ 2δ He isosurfaces have symmetrical toroidal shapes along CF axes; the maximum values of ∇ 2δ He are reached at about 1.5 Å from fluorine atom center in the direction roughly coinciding with the lone pair localization. The absolute values of the ∇ 2δ He could be used to quantify the electron-rich regions of lone pairs. The results are compared with more common visualization methods—3D maps of the molecular electrostatic potential and the electron localization function. We show that a helium atom could be used for evaluation of fine features of molecular electronic shell, since 3He NMR spectral characteristics remain sensitive at relatively large distances.
KW - He NMR
KW - electronic structure
KW - lone pairs
KW - HYDROGEN
KW - LOCALIZATION
KW - He-3 NMR
KW - FULLERENE
KW - COMPLEXES
KW - SYSTEMS
KW - AROMATICITY PROBE
KW - LONE-PAIR
KW - HE-3 NMR
UR - http://www.scopus.com/inward/record.url?scp=85056477691&partnerID=8YFLogxK
UR - http://doi.wiley.com/10.1002/jcc.25585
UR - http://www.mendeley.com/research/outer-electronic-shell-visualization-nmr-chemical-shift-laplacian-helium-probe
U2 - 10.1002/jcc.25585
DO - 10.1002/jcc.25585
M3 - Article
VL - 39
SP - 2459
EP - 2462
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 29
ER -
ID: 36091816