A Mn Bipyrimidine Catalyst Predicted to Reduce CO2 at Lower Overpotential

ACS Catalysis

Volumn 5, Issue 4, 2015, Pages 2521-2528

  Lam, Yan Choi ^a   Nielsen, Robert J ^a   Gray, Harry B ^b   Goddard, William A ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^b CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

chemoselectivity; density functional theory; electrochemical CO2 reduction; overpotential; reaction mechanism

Indexed keywords

ACTIVATION ENERGY; CARBON DIOXIDE; CHEMICAL ACTIVATION; DENSITY FUNCTIONAL THEORY; ELECTROLYTIC REDUCTION; ETHANOL; REACTION KINETICS; REDUCTION; THERMODYNAMICS;

CHEMO-SELECTIVITY; ELECTROCHEMICAL REDUCTIONS; ONE-ELECTRON REDUCTIONS; OVERPOTENTIAL; PRODUCT SELECTIVITIES; REACTION MECHANISM; REACTION THERMODYNAMICS; STANDARD REDUCTION POTENTIALS;

MANGANESE;

EID: 84926430379     PISSN: 21555435     EISSN: None     Source Type: Journal    
DOI: 10.1021/cs501963v     Document Type: Article

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50. -] is no more than 40 mM (since two molecules are produced for every molecule of CO formed).
51. Open shell singlet calculations were performed by obtaining the triplet wave function, then changing the α HOMO into a β orbital and reoptimizing the wave function and geometry. This resulted in a singlet configuration in which the ligand-based electron is antiferromagnetically coupled to an overlapping Mn-based electron. Closed-shell singlet calculations were performed using the RDFT formalism. Since the DFT-computed energy of the open-shell singlet is an upper bound on the energy of the true (spin-uncontaminated) singlet, the latter is lower in energy than the closed-shell singlet.
52. 0, is 1 atm or ca. 0.28 M in acetonitrile.