Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer
Abstract
A solar-driven conversion of CO2 into fuels by artificial photosynthesis would not only mitigate the greenhouse effect but also provide an alternative to obtain fuels in a renewable fashion. To this end, the new iron polypyridine catalyst [Fe(bpyNHEtPY2Me)L2]2+ (L = H2O, CH3CN) was recently developed for the electrochemical reduction of CO2 to CO. Here, we performed density functional theory (DFT) electronic structure calculations to shed light on a possible pathway for CO2 reduction and the origin of the selectivity between CO2 reduction versus the hydrogen evolution reaction. The metal center remains Lewis acidic throughout the reduction process due to ligand loss and mainly ligand-based reduction stabilized by antiferromagnetic coupling to a high-spin Fe(II) center. This results in a high barrier for hydride formation but a facile addition and activation of CO2 via an η2 coordination and stabilizing hydrogen bonding by the amine group. The second unoccupied equatorial coordination site opens up the possibility for an intramolecular protonation with a coordinated water ligand. This facilitates protonation because not only CO2 but also the proton source H2O is activated and properly aligned for a proton transfer due to the Fe-OH2 bond; consequently, both protonation steps are facile. The moderate ligand field allowsmore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); State Univ. of New York (SUNY), Binghamton, NY (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1737618
- Grant/Contract Number:
- AC02-05CH11231; SC0004993; 101528-002
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 12; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Loipersberger, Matthias, Zee, David Z., Panetier, Julien A., Chang, Christopher J., Long, Jeffrey R., and Head-Gordon, Martin. Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.0c00454.
Loipersberger, Matthias, Zee, David Z., Panetier, Julien A., Chang, Christopher J., Long, Jeffrey R., & Head-Gordon, Martin. Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer. United States. https://doi.org/10.1021/acs.inorgchem.0c00454
Loipersberger, Matthias, Zee, David Z., Panetier, Julien A., Chang, Christopher J., Long, Jeffrey R., and Head-Gordon, Martin. Wed .
"Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer". United States. https://doi.org/10.1021/acs.inorgchem.0c00454. https://www.osti.gov/servlets/purl/1737618.
@article{osti_1737618,
title = {Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer},
author = {Loipersberger, Matthias and Zee, David Z. and Panetier, Julien A. and Chang, Christopher J. and Long, Jeffrey R. and Head-Gordon, Martin},
abstractNote = {A solar-driven conversion of CO2 into fuels by artificial photosynthesis would not only mitigate the greenhouse effect but also provide an alternative to obtain fuels in a renewable fashion. To this end, the new iron polypyridine catalyst [Fe(bpyNHEtPY2Me)L2]2+ (L = H2O, CH3CN) was recently developed for the electrochemical reduction of CO2 to CO. Here, we performed density functional theory (DFT) electronic structure calculations to shed light on a possible pathway for CO2 reduction and the origin of the selectivity between CO2 reduction versus the hydrogen evolution reaction. The metal center remains Lewis acidic throughout the reduction process due to ligand loss and mainly ligand-based reduction stabilized by antiferromagnetic coupling to a high-spin Fe(II) center. This results in a high barrier for hydride formation but a facile addition and activation of CO2 via an η2 coordination and stabilizing hydrogen bonding by the amine group. The second unoccupied equatorial coordination site opens up the possibility for an intramolecular protonation with a coordinated water ligand. This facilitates protonation because not only CO2 but also the proton source H2O is activated and properly aligned for a proton transfer due to the Fe-OH2 bond; consequently, both protonation steps are facile. The moderate ligand field allows a rapid ligand exchange for a second intramolecular protonation step and facilitates an exergonic CO release. The lower selectivity of the related [Fe(bpyOHPY2Me)L2]2+ complex can be related to its more acidic second coordination sphere, which enables an intramolecular proton transfer that is kinetically competitive with CO2 addition.},
doi = {10.1021/acs.inorgchem.0c00454},
journal = {Inorganic Chemistry},
number = 12,
volume = 59,
place = {United States},
year = {Wed May 27 00:00:00 EDT 2020},
month = {Wed May 27 00:00:00 EDT 2020}
}
Works referenced in this record:
Chemical approaches to artificial photosynthesis
journal, September 2012
- Concepcion, J. J.; House, R. L.; Papanikolas, J. M.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
Chemical Approaches to Artificial Photosynthesis. 2
journal, October 2005
- Alstrum-Acevedo, James H.; Brennaman, M. Kyle; Meyer, Thomas J.
- Inorganic Chemistry, Vol. 44, Issue 20
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013
- Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
- Chemical Reviews, Vol. 113, Issue 8
Direct and Reversible Hydrogenation of CO2 to Formate by a Bacterial Carbon Dioxide Reductase
journal, December 2013
- Schuchmann, K.; Muller, V.
- Science, Vol. 342, Issue 6164
Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011
- Wang, Wei; Wang, Shengping; Ma, Xinbin
- Chemical Society Reviews, Vol. 40, Issue 7
Photocatalytic Reduction of CO 2 on TiO 2 and Other Semiconductors
journal, June 2013
- Habisreutinger, Severin N.; Schmidt-Mende, Lukas; Stolarczyk, Jacek K.
- Angewandte Chemie International Edition, Vol. 52, Issue 29
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels
journal, January 2014
- Qiao, Jinli; Liu, Yuyu; Hong, Feng
- Chem. Soc. Rev., Vol. 43, Issue 2
Progress in catalyst exploration for heterogeneous CO 2 reduction and utilization: a critical review
journal, January 2017
- Zhao, Guixia; Huang, Xiubing; Wang, Xiangxue
- J. Mater. Chem. A, Vol. 5, Issue 41
A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO 2
journal, June 2016
- Verma, Sumit; Kim, Byoungsu; Jhong, Huei-Ru “Molly”
- ChemSusChem, Vol. 9, Issue 15
“Catalysis in the Refining of Fischer-Tropsch Syncrude”
journal, October 2011
- Brown, Stewart
- Platinum Metals Review, Vol. 55, Issue 4
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012
- Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
- Energy & Environmental Science, Vol. 5, Issue 5
Controlling H + vs CO 2 Reduction Selectivity on Pb Electrodes
journal, November 2014
- Lee, Chang Hoon; Kanan, Matthew W.
- ACS Catalysis, Vol. 5, Issue 1
Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016
- Goodpaster, Jason D.; Bell, Alexis T.; Head-Gordon, Martin
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 8
Efficient Conversion of CO 2 to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts
journal, April 2015
- Medina-Ramos, Jonnathan; Pupillo, Rachel C.; Keane, Thomas P.
- Journal of the American Chemical Society, Vol. 137, Issue 15
Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products
journal, January 2018
- Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin
- ACS Catalysis, Vol. 8, Issue 2
Manganese as a Substitute for Rhenium in CO 2 Reduction Catalysts: The Importance of Acids
journal, February 2013
- Smieja, Jonathan M.; Sampson, Matthew D.; Grice, Kyle A.
- Inorganic Chemistry, Vol. 52, Issue 5
Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO 2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center
journal, August 2015
- Chen, Lingjing; Guo, Zhenguo; Wei, Xi-Guang
- Journal of the American Chemical Society, Vol. 137, Issue 34
Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid
journal, March 2017
- Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques
- Journal of the American Chemical Society, Vol. 139, Issue 10
CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine
journal, August 2019
- Wang, Min; Torbensen, Kristian; Salvatore, Danielle
- Nature Communications, Vol. 10, Issue 1
A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
journal, October 2012
- Costentin, Cyrille; Drouet, Samuel; Robert, Marc
- Science, Vol. 338, Issue 6103
Electrocatalytic reduction of carbon dioxide by nickel cyclam2+ in water: study of the factors affecting the efficiency and the selectivity of the process
journal, November 1986
- Beley, Marc.; Collin, Jean Paul.; Ruppert, Romain.
- Journal of the American Chemical Society, Vol. 108, Issue 24
Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO 2 Reduction
journal, November 2016
- Takeda, Hiroyuki; Cometto, Claudio; Ishitani, Osamu
- ACS Catalysis, Vol. 7, Issue 1
Electroreduction of CO 2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center
journal, July 2017
- Wu, Yueshen; Jiang, Jianbing; Weng, Zhe
- ACS Central Science, Vol. 3, Issue 8
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water
journal, August 2015
- Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao
- Science, Vol. 349, Issue 6253
Fe-Porphyrin-Based Metal–Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO 2
journal, September 2015
- Hod, Idan; Sampson, Matthew D.; Deria, Pravas
- ACS Catalysis, Vol. 5, Issue 11
Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide
journal, October 2015
- Kornienko, Nikolay; Zhao, Yingbo; Kley, Christopher S.
- Journal of the American Chemical Society, Vol. 137, Issue 44
Versatile functionalization of carbon electrodes with a polypyridine ligand: metallation and electrocatalytic H + and CO 2 reduction
journal, January 2015
- Elgrishi, Noémie; Griveau, Sophie; Chambers, Matthew B.
- Chemical Communications, Vol. 51, Issue 14
Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction
journal, February 2016
- Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T.
- Journal of the American Chemical Society, Vol. 138, Issue 6
Molecular electrocatalysts can mediate fast, selective CO 2 reduction in a flow cell
journal, July 2019
- Ren, Shaoxuan; Joulié, Dorian; Salvatore, Danielle
- Science, Vol. 365, Issue 6451
Photochemical and Photoelectrochemical Reduction of CO 2
journal, May 2012
- Kumar, Bhupendra; Llorente, Mark; Froehlich, Jesse
- Annual Review of Physical Chemistry, Vol. 63, Issue 1
Re(bipy-tBu)(CO) 3 Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies
journal, October 2010
- Smieja, Jonathan M.; Kubiak, Clifford P.
- Inorganic Chemistry, Vol. 49, Issue 20
Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
journal, May 2012
- Smieja, J. M.; Benson, E. E.; Kumar, B.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO 2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry
journal, March 2013
- Benson, Eric E.; Sampson, Matthew D.; Grice, Kyle A.
- Angewandte Chemie International Edition, Vol. 52, Issue 18
Direct observation of the reduction of carbon dioxide by rhenium bipyridine catalysts
journal, January 2013
- Sampson, Matthew D.; Froehlich, Jesse D.; Smieja, Jonathan M.
- Energy & Environmental Science, Vol. 6, Issue 12
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis
journal, February 2014
- Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A.
- Journal of the American Chemical Society, Vol. 136, Issue 14
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry
journal, April 2014
- Machan, Charles W.; Sampson, Matthew D.; Chabolla, Steven A.
- Organometallics, Vol. 33, Issue 18
Electrocatalytic Reduction of Carbon Dioxide by Mn(CN)(2,2′-bipyridine)(CO) 3 : CN Coordination Alters Mechanism
journal, August 2015
- Machan, Charles W.; Stanton, Charles J.; Vandezande, Jonathon E.
- Inorganic Chemistry, Vol. 54, Issue 17
Synergistic Effects of Imidazolium-Functionalization on fac -Mn(CO) 3 Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction
journal, March 2019
- Sung, Siyoung; Li, Xiaohui; Wolf, Lucienna M.
- Journal of the American Chemical Society, Vol. 141, Issue 16
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO 2 Reduction by fac -Re(bpy)(CO) 3 Cl
journal, October 2013
- Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P.
- Journal of the American Chemical Society, Vol. 135, Issue 42
Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide
journal, November 2014
- Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M.
- Journal of the American Chemical Society, Vol. 136, Issue 46
Influence of Weak Brønsted Acids on Electrocatalytic CO 2 Reduction by Manganese and Rhenium Bipyridine Catalysts
journal, January 2015
- Riplinger, Christoph; Carter, Emily A.
- ACS Catalysis, Vol. 5, Issue 2
The Mechanism of Homogeneous CO 2 Reduction by Ni(cyclam): Product Selectivity, Concerted Proton–Electron Transfer and C–O Bond Cleavage
journal, June 2014
- Song, Jinshuai; Klein, Eric L.; Neese, Frank
- Inorganic Chemistry, Vol. 53, Issue 14
Kinetics of CO Addition to Ni(cyclam) + in Aqueous Solution
journal, January 1996
- Kelly, Craig A.; Mulazzani, Quinto G.; Blinn, Elliott L.
- Inorganic Chemistry, Vol. 35, Issue 18
The Homogeneous Reduction of CO 2 by [Ni(cyclam)] + : Increased Catalytic Rates with the Addition of a CO Scavenger
journal, March 2015
- Froehlich, Jesse D.; Kubiak, Clifford P.
- Journal of the American Chemical Society, Vol. 137, Issue 10
Ultraefficient homogeneous catalyst for the CO 2 -to-CO electrochemical conversion
journal, October 2014
- Costentin, Cyrille; Passard, Guillaume; Robert, Marc
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO 2 Reduction
journal, April 2017
- Römelt, Christina; Song, Jinshuai; Tarrago, Maxime
- Inorganic Chemistry, Vol. 56, Issue 8
Molecular catalysis of the electrochemical and photochemical reduction of CO2 with Fe and Co metal based complexes. Recent advances
journal, March 2017
- Bonin, Julien; Maurin, Antoine; Robert, Marc
- Coordination Chemistry Reviews, Vol. 334
Mechanisms of catalytic reduction of CO 2 with heme and nonheme metal complexes
journal, January 2018
- Fukuzumi, Shunichi; Lee, Yong-Min; Ahn, Hyun S.
- Chemical Science, Vol. 9, Issue 28
CO 2 Reduction on an Iron-Porphyrin Center: A Computational Study
journal, July 2019
- Davethu, Paul A.; de Visser, Sam P.
- The Journal of Physical Chemistry A, Vol. 123, Issue 30
Pendant Acid–Base Groups in Molecular Catalysts: H-Bond Promoters or Proton Relays? Mechanisms of the Conversion of CO 2 to CO by Electrogenerated Iron(0)Porphyrins Bearing Prepositioned Phenol Functionalities
journal, August 2014
- Costentin, Cyrille; Passard, Guillaume; Robert, Marc
- Journal of the American Chemical Society, Vol. 136, Issue 33
Proton-Coupled Electron Transfer Cleavage of Heavy-Atom Bonds in Electrocatalytic Processes. Cleavage of a C–O Bond in the Catalyzed Electrochemical Reduction of CO 2
journal, June 2013
- Costentin, Cyrille; Drouet, Samuel; Passard, Guillaume
- Journal of the American Chemical Society, Vol. 135, Issue 24
Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction
journal, June 2019
- Nichols, Asa W.; Machan, Charles W.
- Frontiers in Chemistry, Vol. 7
A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO 2 and a Proton Donor Promotes the Electrochemical Reduction of CO 2 to CO Catalyzed by a Rhenium Bipyridine-Type Complex
journal, September 2018
- Haviv, Eynat; Azaiza-Dabbah, Dima; Carmieli, Raanan
- Journal of the American Chemical Society, Vol. 140, Issue 39
Visible-Light-Driven Photocatalytic CO 2 Reduction by a Ni(II) Complex Bearing a Bioinspired Tetradentate Ligand for Selective CO Production
journal, May 2017
- Hong, Dachao; Tsukakoshi, Yuto; Kotani, Hiroaki
- Journal of the American Chemical Society, Vol. 139, Issue 19
Bio-Inspired Mn(I) Complexes for the Hydrogenation of CO 2 to Formate and Formamide
journal, May 2017
- Dubey, Abhishek; Nencini, Luca; Fayzullin, Robert R.
- ACS Catalysis, Vol. 7, Issue 6
Minimal Proton Channel Enables H 2 Oxidation and Production with a Water-Soluble Nickel-Based Catalyst
journal, November 2013
- Dutta, Arnab; Lense, Sheri; Hou, Jianbo
- Journal of the American Chemical Society, Vol. 135, Issue 49
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst
journal, June 2011
- Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H.
- Journal of the American Chemical Society, Vol. 133, Issue 24
Turning on the Protonation-First Pathway for Electrocatalytic CO 2 Reduction by Manganese Bipyridyl Tricarbonyl Complexes
journal, February 2017
- Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani
- Journal of the American Chemical Society, Vol. 139, Issue 7
Development of Molecular Electrocatalysts for Energy Storage
journal, February 2014
- DuBois, Daniel L.
- Inorganic Chemistry, Vol. 53, Issue 8
Positional effects of second-sphere amide pendants on electrochemical CO 2 reduction catalyzed by iron porphyrins
journal, January 2018
- Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K.
- Chemical Science, Vol. 9, Issue 11
Tuning Second Coordination Sphere Interactions in Polypyridyl–Iron Complexes to Achieve Selective Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide
journal, March 2020
- Zee, David Z.; Nippe, Michael; King, Amanda E.
- Inorganic Chemistry, Vol. 59, Issue 7
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014
- Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny
- Molecular Physics, Vol. 113, Issue 2
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008
- Chai, Jeng-Da; Head-Gordon, Martin
- Physical Chemistry Chemical Physics, Vol. 10, Issue 44
ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation
journal, June 2016
- Mardirossian, Narbe; Head-Gordon, Martin
- The Journal of Chemical Physics, Vol. 144, Issue 21
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals
journal, April 2017
- Mardirossian, Narbe; Head-Gordon, Martin
- Molecular Physics, Vol. 115, Issue 19
Assessment of DFT Methods for Transition Metals with the TMC151 Compilation of Data Sets and Comparison with Accuracies for Main-Group Chemistry
journal, April 2019
- Chan, Bun; Gill, Peter M. W.; Kimura, Masanari
- Journal of Chemical Theory and Computation, Vol. 15, Issue 6
A new method for incorporating solvent effect into the classical, ab initio molecular orbital and density functional theory frameworks for arbitrary shape cavity
journal, June 1995
- Truong, Thanh N.; Stefanovich, Eugene V.
- Chemical Physics Letters, Vol. 240, Issue 4
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
The ORCA program system: The ORCA program system
journal, June 2011
- Neese, Frank
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
Optimized accurate auxiliary basis sets for RI-MP2 and RI-CC2 calculations for the atoms Rb to Rn
journal, January 2007
- Hellweg, Arnim; Hättig, Christof; Höfener, Sebastian
- Theoretical Chemistry Accounts, Vol. 117, Issue 4
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide
journal, January 2007
- Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 111, Issue 2
Reduction of Systematic Uncertainty in DFT Redox Potentials of Transition-Metal Complexes
journal, March 2012
- Konezny, Steven J.; Doherty, Mark D.; Luca, Oana R.
- The Journal of Physical Chemistry C, Vol. 116, Issue 10
Accurate p K a Calculations for Carboxylic Acids Using Complete Basis Set and Gaussian-n Models Combined with CPCM Continuum Solvation Methods
journal, August 2001
- Liptak, Matthew D.; Shields, George C.
- Journal of the American Chemical Society, Vol. 123, Issue 30
A Computational Study of the Mechanism of Hydrogen Evolution by Cobalt(Diimine-Dioxime) Catalysts
journal, September 2013
- Bhattacharjee, Anirban; Andreiadis, Eugen S.; Chavarot-Kerlidou, Murielle
- Chemistry - A European Journal, Vol. 19, Issue 45
Acidities of strong neutral Brønsted acids in different media: ACIDITIES OF STRONG NEUTRAL BRØNSTED ACIDS
journal, May 2012
- Raamat, Elin; Kaupmees, Karl; Ovsjannikov, Gea
- Journal of Physical Organic Chemistry, Vol. 26, Issue 2
Unified Benchmarking of Electrocatalysts in Noninnocent Second Coordination Spheres for CO 2 Reduction
journal, July 2019
- Matsubara, Yasuo
- ACS Energy Letters, Vol. 4, Issue 8
Quantum-Chemical Predictions of Absolute Standard Redox Potentials of Diverse Organic Molecules and Free Radicals in Acetonitrile
journal, May 2005
- Fu, Yao; Liu, Lei; Yu, Hai-Zhu
- Journal of the American Chemical Society, Vol. 127, Issue 19
Calculation of One-Electron Redox Potentials Revisited. Is It Possible to Calculate Accurate Potentials with Density Functional Methods?
journal, June 2009
- Roy, Lindsay E.; Jakubikova, Elena; Guthrie, M. Graham
- The Journal of Physical Chemistry A, Vol. 113, Issue 24
Theoretical Studies on the Redox Potentials of Fe Dinuclear Complexes as Models for Hydrogenase
journal, October 2008
- Roy, Lindsay E.; Batista, Enrique R.; Hay, P. Jeffrey
- Inorganic Chemistry, Vol. 47, Issue 20
Catalytic hydrogen production by a Ni–Ru mimic of NiFe hydrogenases involves a proton-coupled electron transfer step
journal, January 2013
- Canaguier, Sigolène; Fourmond, Vincent; Perotto, Carlo U.
- Chemical Communications, Vol. 49, Issue 44
Assertion and validation of the performance of the B3LYP⋆ functional for the first transition metal row and the G2 test set
journal, September 2002
- Salomon, Oliver; Reiher, Markus; Hess, Bernd Artur
- The Journal of Chemical Physics, Vol. 117, Issue 10
Accurate Spin-State Energies for Iron Complexes
journal, November 2008
- Swart, Marcel
- Journal of Chemical Theory and Computation, Vol. 4, Issue 12
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
Theoretical Study of Spin Crossover in 30 Iron Complexes
journal, February 2016
- Kepp, Kasper P.
- Inorganic Chemistry, Vol. 55, Issue 6
Assessment of density functional theory for iron(II) molecules across the spin-crossover transition
journal, September 2012
- Droghetti, A.; Alfè, D.; Sanvito, S.
- The Journal of Chemical Physics, Vol. 137, Issue 12
Assessment of electronic structure methods for the determination of the ground spin states of Fe( ii ), Fe( iii ) and Fe( iv ) complexes
journal, January 2017
- Verma, Pragya; Varga, Zoltan; Klein, Johannes E. M. N.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 20
Highly Selective Molecular Catalysts for the CO 2 -to-CO Electrochemical Conversion at Very Low Overpotential. Contrasting Fe vs Co Quaterpyridine Complexes upon Mechanistic Studies
journal, March 2018
- Cometto, Claudio; Chen, Lingjing; Lo, Po-Kam
- ACS Catalysis, Vol. 8, Issue 4
(η 2 -Acetonitrile)bis(η 5 -cyclopentadienyl)molybdenum( II ):the first structurally characterized complex containing an η 2 -nitrile ligand
journal, January 1986
- Wright, Thomas C.; Wilkinson, Geoffrey; Motevalli, Majid
- J. Chem. Soc., Dalton Trans., Issue 9
Crystal structure of an .eta.2-acetonitrile complex of tungsten(II): acetonitrile as a four-electron donor
journal, October 1991
- Barrera, Joseph; Sabat, Michal; Harman, W. Dean
- Journal of the American Chemical Society, Vol. 113, Issue 21
Reversible Cleavage of Carbon−Carbon Bonds in Benzonitrile Using Nickel(0)
journal, December 2000
- Garcia, Juventino J.; Jones, William D.
- Organometallics, Vol. 19, Issue 26
Formation of .eta.2-side-bonded aryl nitrile complexes from 4-metallaisoxazolin-5-one species and their application in the thermal and photochemical activation of carbon-hydrogen bonds
journal, March 1988
- Chetcuti, Peter A.; Knobler, Carolyn B.; Hawthorne, M. Frederick
- Organometallics, Vol. 7, Issue 3
Alkyne and Nitrile as η 2 (3e) Ligands in [Tris(pyrazolyl)borato]niobium(I) Complexes. Synthesis, Structure, and Coupling Reaction
journal, January 1996
- Lorente, Philippe; Carfagna, Carla; Etienne, Michel
- Organometallics, Vol. 15, Issue 4
How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study
journal, April 2015
- Butschke, Burkhard; Fillman, Kathlyn L.; Bendikov, Tatyana
- Inorganic Chemistry, Vol. 54, Issue 10
On the Innocence of Bipyridine Ligands: How Well Do DFT Functionals Fare for These Challenging Spin Systems?
journal, November 2013
- Milko, Petr; Iron, Mark A.
- Journal of Chemical Theory and Computation, Vol. 10, Issue 1
Entangled Electrons Foil Synthesis of Elusive Low-Valent Vanadium Oxo Complex
journal, January 2016
- Schlimgen, Anthony W.; Heaps, Charles W.; Mazziotti, David A.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 4
Multireference Electronic Structures of Fe–Pyridine(diimine) Complexes over Multiple Oxidation States
journal, July 2017
- Ortuño, Manuel A.; Cramer, Christopher J.
- The Journal of Physical Chemistry A, Vol. 121, Issue 31
Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals
journal, August 2017
- Sayfutyarova, Elvira R.; Sun, Qiming; Chan, Garnet Kin-Lic
- Journal of Chemical Theory and Computation, Vol. 13, Issue 9
Active Space Selection Based on Natural Orbital Occupation Numbers from n -Electron Valence Perturbation Theory
journal, April 2019
- Khedkar, Abhishek; Roemelt, Michael
- Journal of Chemical Theory and Computation, Vol. 15, Issue 6
Automated Selection of Active Orbital Spaces
journal, March 2016
- Stein, Christopher J.; Reiher, Markus
- Journal of Chemical Theory and Computation, Vol. 12, Issue 4
Automated Identification of Relevant Frontier Orbitals for Chemical Compounds and Processes
journal, April 2017
- Stein, ChristopherJ.; Reiher, Markus
- CHIMIA International Journal for Chemistry, Vol. 71, Issue 4
autoCAS : A Program for Fully Automated Multiconfigurational Calculations
journal, June 2019
- Stein, Christopher J.; Reiher, Markus
- Journal of Computational Chemistry
A New Mode of Activation of CO2 by Metal-Ligand Cooperation with Reversible CC and MO Bond Formation at Ambient Temperature
journal, June 2012
- Vogt, Matthias; Gargir, Moti; Iron, Mark A.
- Chemistry - A European Journal, Vol. 18, Issue 30
Reversible CO 2 binding triggered by metal–ligand cooperation in a rhenium( i ) PNP pincer-type complex and the reaction with dihydrogen
journal, January 2014
- Vogt, Matthias; Nerush, Alexander; Diskin-Posner, Yael
- Chem. Sci., Vol. 5, Issue 5
Rhenium(I) Triscarbonyl Complexes with Redox-Active Amino- and Iminopyridine Ligands: Metal–Ligand Cooperation as Trigger for the Reversible Binding of CO 2 via a Dearmomatization/Rearomatization Reaction Sequence
journal, February 2017
- Stichauer, Rasmus; Helmers, Arne; Bremer, Jennifer
- Organometallics, Vol. 36, Issue 4
Transition Metal Frustrated Lewis Pairs
journal, October 2013
- Flynn, Stephanie R.; Wass, Duncan F.
- ACS Catalysis, Vol. 3, Issue 11
Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO
journal, July 2011
- Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing
- Nature Chemistry, Vol. 3, Issue 8
Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal-Ligand Binding of CO 2
journal, April 2015
- Sieh, Daniel; Lacy, David C.; Peters, Jonas C.
- Chemistry - A European Journal, Vol. 21, Issue 23