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Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields**
Authors:Sergey A Shteingolts  Adam I Stash  Vladimir G Tsirelson  Robert R Fayzullin
Affiliation:1. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, Kazan, 420088 Russian Federation;2. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow, 119991 Russian Federation;3. D.I. Mendeleev University of Chemical Technology, 9 Miusskaya Square, Moscow, 125047 Russian Federation
Abstract:Intricate behaviour of one-electron potentials from the Euler equation for electron density and corresponding gradient force fields in crystals was studied. Channels of locally enhanced kinetic potential and corresponding saddle Lagrange points were found between chemically bonded atoms. Superposition of electrostatic urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0001 and kinetic urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0002 potentials and electron density urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0003 allowed partitioning any molecules and crystals into atomic urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0004 - and potential-based urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0005 -basins; urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0006 -basins explicitly account for the electron exchange effect, which is missed for urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0007 -ones. Phenomena of interatomic charge transfer and related electron exchange were explained in terms of space gaps between zero-flux surfaces of urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0008 - and urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0009 -basins. The gap between urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0010 - and urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0011 -basins represents the charge transfer, while the gap between urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0012 - and urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0013 -basins is a real-space manifestation of sharing the transferred electrons caused by the static exchange and kinetic effects as a response against the electron transfer. The regularity describing relative positions of urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0014 -, urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0015 -, and urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0016 - basin boundaries between interacting atoms was proposed. The position of urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0017 -boundary between urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0018 - and urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0019 -ones within an electron occupier atom determines the extent of transferred electron sharing. The stronger an H???O hydrogen bond is, the deeper hydrogen atom's urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0020 -basin penetrates oxygen atom's urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0021 -basin, while for covalent bonds a urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0022 -boundary closely approaches a urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0023 -one indicating almost complete sharing of the transferred electrons. In the case of ionic bonds, the same region corresponds to electron pairing within the urn:x-wiley:09476539:media:chem202200985:chem202200985-math-0024 -basin of an electron occupier atom.
Keywords:bond theory  electron transfer  electronic structure  exchange effects  quantum crystallography
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