ABSTRACT
Abstract ................................................................................................. 108 3.1 Introduction .................................................................................. 108 3.2 On Quantum Nature of Electronegativity and
Chemical Hardness .......................................................................111 3.3 Semiclassical Analytics of Quantum Evolution Amplitude ..........117 3.3.1 Path Integral Semiclassical Expansion ..............................117 3.3.2 Connected Correlation Functions ..................................... 121 3.3.3 Classical Fluctuation Path and Connected
Green Function ................................................................. 130 3.3.3.1 Calculation of Classical Fluctuation Path ......... 131 3.3.3.2 Calculation of Connected Green Function ........ 133 3.3.4 Second Order for Semiclassical Propagator,
Partition Function and Density ......................................... 136 3.4 Semiclassical Periodicity of Electronegativity and
Chemical Hardness ...................................................................... 140 3.4.1 Fourth Order for Semiclassical Electronegativity
and Chemical Hardness .................................................... 140 3.4.2 Fourth Order for Semiclassical Electronegativity
and Chemical Hardness .................................................... 149 3.5 Conclusion ................................................................................... 158 Keywords .............................................................................................. 160
References ............................................................................................. 160 Author’s Main References ........................................................... 160 Specific References ...................................................................... 161
ABSTRACT
The semiclassical path integral approach is undertaken to develop new definitions and atomic scales of electronegativity and chemical hardness. The considered quantum probability amplitude up to the fourth order expansion provides intrinsic electronegativity and chemical hardness analytical expressions in terms of principal quantum number of the concerned valence shell and of the effective atomic charge including screening effects. The present electronegativity scale strikes on different order of magnitudes down groups of Periodic Table still satisfying the main required acceptability criteria respecting the finite difference based scale. The actual chemical hardness scale improves the trend across periods of Periodic System avoiding the usual irregularities within the old-fashioned energetic picture. The current quest introduces the electronegativity of an element as the power with which the frontier electrons are attracted to the center of the atom being a stability measure of the atomic system as a whole. However, both electronegativity and chemical hardness are analyzed for their quantum nature in Fock spaces of electronic occupancies, while maintaining their dichotomy in observability.
