Systematic treatment of spin-reactivity indicators in conceptual density functional theory

作者：Alain Miranda Quintana Ramon; Ayers Paul W

来源：Theoretical Chemistry Accounts, 2016, 135(10): 1-18.

DOI：10.1007/s00214-016-1995-5

• Conceptual density functional theory
• Spin-reactivity indicators
• Frontier molecular orbital approximation
• Spin-chemical potential
• Spin-hardness
• Spin-philicity

The spin-resolved conceptual density functional theory is presented, emphasizing the finite-difference approximations for spin-reactivity indicators and especially the spin-hardness. We derive simple approximations for these spin-reactivity indicators in terms of Kohn-Sham orbital energies and discuss their accuracy and validity. We also show that the second derivative of the energy with respect to the spin-abundance, N (S) = A1/2M (S) , is nonnegative, contradicting the generally negative values obtained for one of the most popular formulas used to approximate this quantity. A new approximation for the spin-hardness is proposed and assessed based on information for spin-philicities and singlet-triplet gaps. One conclusion of our work is that the tendency in the literature to mix linear models (e.g., one-sided derivatives for chemical potentials and Fukui functions) with quadratic models (e.g., two-sided derivatives for hardnesses and dual descriptors) not only is theoretically unsound, but often leads to chemically absurd results.

• 出版日期2016-9-17