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Title: Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics

Abstract

Density functional theory (DFT) is widely used in transition-metal chemistry, yet essential properties such as spin-state energetics in transition-metal complexes (TMCs) are well known to be sensitive to the choice of the exchange–correlation functional. Increasing the amount of exchange in a functional typically shifts the preferred ground state in first-row TMCs from low-spin to high-spin by penalizing delocalization error, but the effect on properties of second-row complexes is less well known. We compare the exchange sensitivity of adiabatic spin-splitting energies in pairs of mononuclear 3d and 4d mid-row octahedral transition-metal complexes. We analyze hundreds of complexes assembled from four metals in two oxidation states with ten small monodentate ligands that span a wide range of field strengths expected to favor a variety of ground states. We observe consistently lower but proportional sensitivity to exchange fraction among 4d TMCs with respect to their isovalent 3d TMC counterparts, leading to the largest difference in sensitivities for the strongest field ligands. The combined effect of reduced exchange sensitivities and the greater low-spin bias of most 4d TMCs means that while over one-third of 3d TMCs change ground states over a modest variation (ca. 0.0–0.3) in exchange fraction, almost no 4d TMCs do. Differencesmore » in delocalization, as judged through changes in the metal–ligand bond lengths between spin states, do not explain the distinct behavior of 4d TMCs. Instead, evaluation of potential energy curves in 3d and 4d TMCs reveals that higher exchange sensitivities in 3d TMCs are likely due to the opposing effect of exchange on the low-spin and high-spin states, whereas the effect on both spin states is more comparable in 4d TMCs.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Department of Chemical Engineering;Massachusetts Institute of Technology;Cambridge;USA;Department of Chemistry
  2. Department of Chemical Engineering;Massachusetts Institute of Technology;Cambridge;USA
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); National Science Foundation (NSF)
OSTI Identifier:
1648590
Alternate Identifier(s):
OSTI ID: 1713198
Grant/Contract Number:  
SC0018096; N00014-17-1-2956; N00014-18-1-2434; CBET-1704266; 1122374; ACI-1548562
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Volume: 22 Journal Issue: 34; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Nandy, Aditya, Chu, Daniel K., Harper, Daniel R., Duan, Chenru, Arunachalam, Naveen, Cytter, Yael, and Kulik, Heather J. Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0CP02977G.
Nandy, Aditya, Chu, Daniel K., Harper, Daniel R., Duan, Chenru, Arunachalam, Naveen, Cytter, Yael, & Kulik, Heather J. Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics. United Kingdom. https://doi.org/10.1039/D0CP02977G
Nandy, Aditya, Chu, Daniel K., Harper, Daniel R., Duan, Chenru, Arunachalam, Naveen, Cytter, Yael, and Kulik, Heather J. Tue . "Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics". United Kingdom. https://doi.org/10.1039/D0CP02977G.
@article{osti_1648590,
title = {Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics},
author = {Nandy, Aditya and Chu, Daniel K. and Harper, Daniel R. and Duan, Chenru and Arunachalam, Naveen and Cytter, Yael and Kulik, Heather J.},
abstractNote = {Density functional theory (DFT) is widely used in transition-metal chemistry, yet essential properties such as spin-state energetics in transition-metal complexes (TMCs) are well known to be sensitive to the choice of the exchange–correlation functional. Increasing the amount of exchange in a functional typically shifts the preferred ground state in first-row TMCs from low-spin to high-spin by penalizing delocalization error, but the effect on properties of second-row complexes is less well known. We compare the exchange sensitivity of adiabatic spin-splitting energies in pairs of mononuclear 3d and 4d mid-row octahedral transition-metal complexes. We analyze hundreds of complexes assembled from four metals in two oxidation states with ten small monodentate ligands that span a wide range of field strengths expected to favor a variety of ground states. We observe consistently lower but proportional sensitivity to exchange fraction among 4d TMCs with respect to their isovalent 3d TMC counterparts, leading to the largest difference in sensitivities for the strongest field ligands. The combined effect of reduced exchange sensitivities and the greater low-spin bias of most 4d TMCs means that while over one-third of 3d TMCs change ground states over a modest variation (ca. 0.0–0.3) in exchange fraction, almost no 4d TMCs do. Differences in delocalization, as judged through changes in the metal–ligand bond lengths between spin states, do not explain the distinct behavior of 4d TMCs. Instead, evaluation of potential energy curves in 3d and 4d TMCs reveals that higher exchange sensitivities in 3d TMCs are likely due to the opposing effect of exchange on the low-spin and high-spin states, whereas the effect on both spin states is more comparable in 4d TMCs.},
doi = {10.1039/D0CP02977G},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 34,
volume = 22,
place = {United Kingdom},
year = {2020},
month = {9}
}

Journal Article:
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https://doi.org/10.1039/D0CP02977G

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  • Stein, Tamar; Autschbach, Jochen; Govind, Niranjan
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 24
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Understanding and Reducing Errors in Density Functional Calculations
journal, August 2013


Towards quantifying the role of exact exchange in predictions of transition metal complex properties
journal, July 2015

  • Ioannidis, Efthymios I.; Kulik, Heather J.
  • The Journal of Chemical Physics, Vol. 143, Issue 3
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Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO) 3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor
journal, November 2017

  • Hedström, Svante; Chaudhuri, Subhajyoti; La Porte, Nathan T.
  • Journal of the American Chemical Society, Vol. 139, Issue 46
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Density‐functional theory with self‐interaction correction: Application to the lithium molecule a)
journal, March 1985

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  • The Journal of Chemical Physics, Vol. 82, Issue 6
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Ironing out the photochemical and spin-crossover behavior of Fe(II) coordination compounds with computational chemistry
journal, April 2017


Self-Interaction Error in Density Functional Theory: An Appraisal
journal, April 2018

  • Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 9
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Performance of CASPT2 and DFT for Relative Spin-State Energetics of Heme Models
journal, January 2010

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Absorption Spectra of Co-ordination Compounds. I
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Density-Functional Theory of the Energy Gap
journal, November 1983


Density functionals that are one- and two- are not always many-electron self-interaction-free, as shown for H2+, He2+, LiH+, and Ne2+
journal, March 2007

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Incorrect Dissociation Behavior of Radical Ions in Density Functional Calculations
journal, October 1997

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  • The Journal of Physical Chemistry A, Vol. 101, Issue 43
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Computational Ligand Descriptors for Catalyst Design
journal, October 2018


Assessment of Tuned Range Separated Exchange Functionals for Spectroscopies and Properties of Uranium Complexes
journal, July 2017

  • Duignan, Thomas J.; Autschbach, Jochen; Batista, Enrique
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 8
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Physical Content of the Exact Kohn-Sham Orbital Energies: Band Gaps and Derivative Discontinuities
journal, November 1983


The Metal Hydride Problem of Computational Chemistry: Origins and Consequences
journal, March 2019

  • Moltved, Klaus A.; Kepp, Kasper P.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 13
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Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

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One- and many-electron self-interaction error in local and global hybrid functionals
journal, April 2016


The performance of semilocal and hybrid density functionals in 3d transition-metal chemistry
journal, January 2006

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Self-consistent hybrid functional for condensed systems
journal, May 2014


Reversible CO Scavenging via Adsorbate-Dependent Spin State Transitions in an Iron(II)–Triazolate Metal–Organic Framework
journal, April 2016

  • Reed, Douglas A.; Xiao, Dianne J.; Gonzalez, Miguel I.
  • Journal of the American Chemical Society, Vol. 138, Issue 17
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Open Babel: An open chemical toolbox
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Long-range–short-range separation of the electron-electron interaction in density-functional theory
journal, December 2004


A well-tempered density functional theory of electrons in molecules
journal, January 2007

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Toward Accurate Theoretical Thermochemistry of First Row Transition Metal Complexes
journal, December 2011

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Theoretical Study of the Fe(phen) 2 (NCS) 2 Spin-Crossover Complex with Reparametrized Density Functionals
journal, December 2002


The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes
journal, November 2004

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  • Journal of Computational Chemistry, Vol. 25, Issue 15
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Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

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Multiplet splittings and other properties from density functional theory: an assessment in iron–porphyrin systems
journal, January 2005


Iron(II) and Iron(III) Spin Crossover: Toward an Optimal Density Functional
journal, April 2018

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  • The Journal of Physical Chemistry A, Vol. 122, Issue 16
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Ab Initio Calculations for Spin-Gaps of Non-Heme Iron Complexes
journal, June 2019

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  • Journal of Chemical Theory and Computation, Vol. 15, Issue 8
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Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg
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Switching of Molecular Spin States in Inorganic Complexes by Temperature, Pressure, Magnetic Field and Light: Towards Molecular Devices: Switching of Molecular Spin States in Inorganic Complexes
journal, November 2004

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Many-electron self-interaction error in approximate density functionals
journal, November 2006

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Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

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Strategies and Software for Machine Learning Accelerated Discovery in Transition Metal Chemistry
journal, September 2018

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Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

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Delocalization Error and “Functional Tuning” in Kohn–Sham Calculations of Molecular Properties
journal, June 2014

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The Catalyst Genome
journal, December 2012

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Automated in Silico Design of Homogeneous Catalysts
journal, January 2020


Seeing Is Believing: Experimental Spin States from Machine Learning Model Structure Predictions
journal, March 2020

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Prediction of charge-transfer excitations in coumarin-based dyes using a range-separated functional tuned from first principles
journal, December 2009

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Density functional theory for modelling large molecular adsorbate–surface interactions: a mini-review and worked example
journal, November 2016


Guest Tunable Structure and Spin Crossover Properties in a Nanoporous Coordination Framework Material
journal, September 2009

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Molecular Engineering of Photosensitizers for Nanocrystalline Solar Cells:  Synthesis and Characterization of Ru Dyes Based on Phosphonated Terpyridines
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Two-State Reactivity in Organometallic Gas-Phase Ion Chemistry
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Enhanced Cooperativity in Supported Spin-Crossover Metal–Organic Frameworks
journal, July 2017

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A challenge for density functionals: Self-interaction error increases for systems with a noninteger number of electrons
journal, August 1998

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Excitation Gaps of Finite-Sized Systems from Optimally Tuned Range-Separated Hybrid Functionals
journal, April 2012

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Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis
journal, April 2019


Organic Electronic Materials: Recent Advances in the DFT Description of the Ground and Excited States Using Tuned Range-Separated Hybrid Functionals
journal, April 2014

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Systematic Error Estimation for Chemical Reaction Energies
journal, May 2016

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Fundamental and excitation gaps in molecules of relevance for organic photovoltaics from an optimally tuned range-separated hybrid functional
journal, August 2011


Koopmans’ springs to life
journal, December 2009

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