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Title: How far do electrons delocalize?

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4897264· OSTI ID:22436570
;  [1]
  1. Gaussian, Inc., 340 Quinnipiac St., Bldg. 40 , Wallingford, Connecticut 06492 (United States)

Electron delocalization is central to chemical bonding, but it is also a fundamentally nonclassical and nonintuitive quantum mechanical phenomenon. Tools to quantify and visualize electron delocalization help to understand, teach, and predict chemical reactivity. We develop a new approach to quantify and visualize electron delocalization in real space. Our electron delocalization range function EDR(r{sup -vector};u) quantifies the degree to which electrons at point r{sup -vector} in a calculated wavefunction delocalize over length scale u. Its predictions are physically reasonable. For example, EDR(r{sup -vector};u=0.25 bohr) is close to one at points r{sup -vector} in the cores of first-row atoms, consistent with the localization of core electrons to ∼0.25 bohr. EDR(r{sup -vector};u=1 bohr) is close to one at points r{sup -vector} in typical covalent bonds, consistent with electrons delocalizing over the length of the bond. Our approach provides a rich representation of atomic shell structure; covalent and ionic bonding; the delocalization of excited states, defects, and solvated electrons; metallic and insulating systems; and bond stretching and strong correlation.

OSTI ID:
22436570
Journal Information:
Journal of Chemical Physics, Vol. 141, Issue 14; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English