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Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes
Author(s) -
Stauch Tim,
Chakraborty Romit,
HeadGordon Martin
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900853
Subject(s) - spin crossover , chemistry , spin transition , carbon monoxide , octahedron , spin states , hydrostatic pressure , transition metal , ligand (biochemistry) , chemical physics , ligand field theory , crystallography , molecule , inorganic chemistry , crystal structure , thermodynamics , physics , ion , biochemistry , receptor , organic chemistry , catalysis
Spin state switching on external stimuli is a phenomenon with wide applicability, ranging from molecular electronics to gas activation in nanoporous frameworks. Here, we model the spin crossover as a function of the hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first‐row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of the ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a fivefold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe 2+ in [Fe(II)(NH 3 ) 5 CO] 2+ .