scholarly journals Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory

2017 ◽  
Vol 23 (61) ◽  
pp. 15436-15445 ◽  
Author(s):  
Nicholas J. Fowler ◽  
Christopher F. Blanford ◽  
Jim Warwicker ◽  
Sam P. de Visser
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Continuum Electrostatics ◽  
Copper Proteins ◽  
Functional Theory ◽  
Reduction Potentials

scholarly journals Density functional theory (DFT) calculations of VI/V reduction potentials of uranyl coordination complexes in non-aqueous solutions

2019 ◽  
Vol 21 (6) ◽  
pp. 3227-3241 ◽  
Author(s):  
Krishnamoorthy Arumugam ◽  
Neil A. Burton
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Aqueous Solutions ◽  
Density Functional ◽  
Coordination Complexes ◽  
Dft Study ◽  
Redox Behavior ◽  
Functional Theory ◽  
Reduction Potentials ◽  
Uranium Complexes

Of particular interest within the +6 uranium complexes is the linear uranyl(vi) cation and it forms numerous coordination complexes in solution and exhibits incongruent redox behavior depending on coordinating ligands. This DFT study predicts VI/V reduction potentials of a range of uranyl(vi) complexes in non-aqueous solutions within ∼0.10−0.20 eV of experiment.

scholarly journals An Assessment of Long-Range Corrected Density Functional Approximations in the Calculation of the Reduction Potentials of Ni(S2C2H2)2, Ni(Se2C2H2)2, Ni(S2C2H2)(N2C2H4), and Ni(Se2C2H2)(N2C2H4) Complexes

2021 ◽  
Author(s):  
Eric Bushnell ◽  
Jesse Elder
Keyword(s):  
Density Functional Theory ◽  
Standard Deviation ◽  
Long Range ◽  
Density Functional ◽  
Dft Methods ◽  
Functional Theory ◽  
Reduction Potentials ◽  
Redox Couples ◽  
Standard Deviations ◽  
Relative Errors

Herein an assessment of several Long Range Corrected (LRC) Density Functional Theory (DFT) methods for the calculation of reduction potentials of the ([Ni(X2C2H2)2]n/[Ni(X2C2H2)2]n-1), and ([Ni(X2C2H2)(N2C2H4)]n/[Ni(X2C2H2)(N2C2H4)]n-1) and (where X= S or Se and n = 0, or -1) redox couples was done. From the results the values of ω that provide best agreement with CCSD(T) for the tested LRC DFT methods are 0.05 bohr-1, 0.15 bohr-1, 0.05 bohr-1, and 0.20 bohr-1 for ω-B97XD, LC-BLYP, CAM-B3LYP, and ω-B97, respectively. With these values the unsigned average in error was 0.12 V with a standard deviation of 0.13 V for ω-B97XD. For LC-BLYP, CAM-B3LYP, and ω-B97 the unsigned averages in relative errors were 0.12 V, 0.11 V, and 0.13 V, respectively, with respective standard deviations of 0.11 V, 0.12 V and 0.13 V.

scholarly journals Theoretical Study of Divalent Bis(Pentaisopropylcyclopentadienyl) Actinocenes

2019 ◽  
Author(s):  
Jason Yu ◽  
Filipp Furche
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Theoretical Study ◽  
Ground States ◽  
Functional Theory ◽  
Reduction Potentials ◽  
Td Dft ◽  
Mixed Ground ◽  
Divalent Lanthanide ◽  
Linear Coordination

The existence of divalent bis(pentaisopropylcyclopentadienyl) actinocene compounds, An(CpiPr5)2 for An = (Th, U, Pu, Am, Bk, No, Lr), is assessed by density functional theory (DFT) calculations with scalar-relativistic small core pseudopotentials. The calculations predict ground states with significant 6d occupation for Th, U, and Lr, whereas Am, Bk, and No exhibit 5f ground states. A mixed ground state with predominant 5f character is found for Pu. The complexes exhibit a linear coordination geometry and high S10 symmetry except for Pu(CpiPr5)2 and Am(CpiPr5)2, which are found to be bent by 11 and 12 degrees , respectively. Absorption spectra are simulated with time-dependent density functional theory (TD-DFT) and compared to experimental spectra of known tris(C4H4SiMe3) and tris(C5H3(SiMe3)2) compounds [M. E. Fieser et al., J. Am. Chem. Soc. 2015, 137, 369-382] as well as recently synthesized divalent lanthanide analogs Dy(CpiPr5)2 and Tb(CpiPr5)2 [C. Gould et al., J. Am. Chem. Soc. 2019, accepted]. Thermodynamic stability is assessed by calculation of adiabatic reduction potentials of the trivalent precursors [An(CpiPr5 )2] +, and the feasibility of further reduction to obtain as yet unknown monovalent molecular actinide complexes is discussed. <br>

scholarly journals Theoretical Study of Divalent Bis(Pentaisopropylcyclopentadienyl) Actinocenes

2019 ◽  
Author(s):  
Jason Yu ◽  
Filipp Furche
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Theoretical Study ◽  
Ground States ◽  
Functional Theory ◽  
Reduction Potentials ◽  
Td Dft ◽  
Mixed Ground ◽  
Divalent Lanthanide ◽  
Linear Coordination

The existence of divalent bis(pentaisopropylcyclopentadienyl) actinocene compounds, An(CpiPr5)2 for An = (Th, U, Pu, Am, Bk, No, Lr), is assessed by density functional theory (DFT) calculations with scalar-relativistic small core pseudopotentials. The calculations predict ground states with significant 6d occupation for Th, U, and Lr, whereas Am, Bk, and No exhibit 5f ground states. A mixed ground state with predominant 5f character is found for Pu. The complexes exhibit a linear coordination geometry and high S10 symmetry except for Pu(CpiPr5)2 and Am(CpiPr5)2, which are found to be bent by 11 and 12 degrees , respectively. Absorption spectra are simulated with time-dependent density functional theory (TD-DFT) and compared to experimental spectra of known tris(C4H4SiMe3) and tris(C5H3(SiMe3)2) compounds [M. E. Fieser et al., J. Am. Chem. Soc. 2015, 137, 369-382] as well as recently synthesized divalent lanthanide analogs Dy(CpiPr5)2 and Tb(CpiPr5)2 [C. Gould et al., J. Am. Chem. Soc. 2019, accepted]. Thermodynamic stability is assessed by calculation of adiabatic reduction potentials of the trivalent precursors [An(CpiPr5 )2] +, and the feasibility of further reduction to obtain as yet unknown monovalent molecular actinide complexes is discussed. <br>

scholarly journals Benchmark study of the performance of density functional theory for reduction potentials of vanadium compounds

2020 ◽  
pp. 14-21
Author(s):  
Samat Tussupbayev ◽  
Gulnar Kudaibergenova
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Vanadium Redox Flow Battery ◽  
Hybrid Functional ◽  
Vanadium Compounds ◽  
Functional Theory ◽  
Hartree Fock ◽  
Benchmark Study ◽  
Reduction Potentials ◽  
Hybrid Functionals

A systematic benchmark study was performed for the first time to investigate the performance of density functional theory for calculation of reduction potentials of vanadium compounds. Six density functionals of different types were selected for testing: local OLYP and M06L, global hybrid O3LYP and B3LYP, as well as, meta-hybrid functionals TPSSh and M06. Local and hybrid functionals with a relatively high contribution of Hartree-Fock exchange showed unsatisfactory results. In particular, the widely used hybrid functional B3LYP for the transformation VIII→VII occurring in the vanadium redox flow battery yields a negative value of the standard potential instead of a positive one. Among the tested functionals the smallest deviation from the experimental data provides the meta-hybrid functional TPSSh with a 10% contribution of the Hartree-Fock exchange. The computational protocol to calculate redox potentials of vanadium compounds is suggested.

Asn47 and Phe114 modulate the inner sphere reorganization energies of type zero copper proteins

2016 ◽  
Vol 18 (25) ◽  
pp. 16748-16756 ◽  
Author(s):  
Biswajit Sadhu ◽  
Mahesh Sundararajan
Keyword(s):  
Density Functional Theory ◽  
Amino Acid ◽  
Density Functional ◽  
Copper Proteins ◽  
Amino Acid Residues ◽  
Functional Theory ◽  
Copper Protein ◽  
Inner Sphere ◽  
Reorganization Energies

Density functional theory based calculations predict the inner sphere reorganization energies of type zero copper protein is largely modulated by Asn47 and Phe114 amino acid residues.

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