The chemical hardness of molecules and the band gap of solids within charge equilibration formalisms |
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Authors: | M H Müser |
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Institution: | 1.Jülich Supercomputer Centre,Institute for Advanced Simulation,Jülich,Germany |
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Abstract: | This work finds that different charge equilibration methods lead to qualitatively different responses of molecules and solids
to an excess charge. The investigated approaches are the regular charge equilibration (QE), the atom-atom-charge transfer
(AACT), and the split-charge equilibration (SQE) method. In QE, the hardness of molecules and the band gap of solids approaches
zero at large particle numbers, affirming the claim that QE induces metallic behavior. AACT suffers from producing negative
values of the hardness; moreover valence and conduction bands of solids cross. In contrast to these methods, SQE can reproduce
the generic behavior of dielectric molecules or solids. Moreover, first quantitative results for the NaCl molecule are promising.
The results derived in this work may have beneficial implications for the modeling of redox reactions. They reveal that by
introducing formal oxidation states into force field-based simulations it will become possible to simulate redox reactions
including non-equilibrium contact electrification, voltage-driven charging of galvanic cells, and the formation of zwitterionic
molecules. |
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Keywords: | |
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