Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

Stauch, Tim; Chakraborty, Romit; Head‐Gordon, Martin

doi:10.1002/cphc.201900853

Title: Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

Journal Article · 20 September 2019 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.201900853 · OSTI ID:1580969

^[1]; Chakraborty, Romit ^[2]; Head‐Gordon, Martin ^[3]

Univ. of Bremen (Germany). Inst. for Physical and Theoretical Chemistry; Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry
Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

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 Fe²⁺ in [Fe(II)(NH₃)₅ CO]²⁺.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); German Research Foundation (DFG)

Grant/Contract Number:: AC02-05CH11231; STA 1526/1-1; STA 1526/2-1

OSTI ID:: 1580969

Journal Information:: ChemPhysChem, Vol. 20, Issue 21; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
density functional theory
metal-ligand complexes
pressure
quantum chemical modeling
spin crossover

Title: Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes

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