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Updated: Jul 14, 2026
Thermochemical Studies of Ni(II) and Zn(II) Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Looking for a double-hybrid recipe to accurately predict spin-state energy gaps of transition metal complexes
Muhammad Irfan1,2, Lucas V Besteiro1,2, Éric Brémond3
1CINBIO, Universidade de Vigo, 36310 Vigo, Spain.
Abstract:
We assess the performance of double-hybrid density functionals for spin-state energetics and state ordering in transition-metal complexes using the SSE17 dataset composed of 17 experimental references. Among the eight double hybrids examined, B2-PLYP emerges as the only approach combining robust accuracy and reliability, particularly for the challenging spin-crossover (SCO) complexes. By analyzing the interplay between exact-like exchange (EXX) and PT2 correlation contributions, we show that successful double hybrids follow a quadratic relation between the two fractions (ac=ax2). Finally, an analysis of a representative iron SCO complex further reveals that increasing PT2 correlation and/or decreasing EXX enhances ligand-to-metal σ-donation, highlighting the need for a balanced treatment of both terms.
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