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

Abstract

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+.

Authors:
ORCiD logo [1];  [2];  [3]
  1. Univ. of Bremen (Germany). Inst. for Physical and Theoretical Chemistry; Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry
  2. 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
  3. 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
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); German Research Foundation (DFG)
OSTI Identifier:
1580969
Grant/Contract Number:  
AC02-05CH11231; STA 1526/1-1; STA 1526/2-1
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 20; Journal Issue: 21; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; metal-ligand complexes; pressure; quantum chemical modeling; spin crossover

Citation Formats

Stauch, Tim, Chakraborty, Romit, and Head‐Gordon, Martin. Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes. United States: N. p., 2019. Web. https://doi.org/10.1002/cphc.201900853.
Stauch, Tim, Chakraborty, Romit, & Head‐Gordon, Martin. Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes. United States. https://doi.org/10.1002/cphc.201900853
Stauch, Tim, Chakraborty, Romit, and Head‐Gordon, Martin. Fri . "Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes". United States. https://doi.org/10.1002/cphc.201900853. https://www.osti.gov/servlets/purl/1580969.
@article{osti_1580969,
title = {Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes},
author = {Stauch, Tim and Chakraborty, Romit and Head‐Gordon, Martin},
abstractNote = {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+.},
doi = {10.1002/cphc.201900853},
journal = {ChemPhysChem},
number = 21,
volume = 20,
place = {United States},
year = {2019},
month = {9}
}

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