scholarly journals Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO2 reduction catalysts

2021 ◽  
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Kareesa J. Kron ◽  
Jeffrey S. Derrick ◽  
Christopher J. Chang ◽  
...  
Keyword(s):  
Decomposition Analysis ◽  
Co2 Reduction ◽  
Energy Decomposition Analysis ◽  
Continuum Solvation ◽  
Energy Decomposition ◽  
Analysis Theory ◽  
Reduction Catalysts

Extension of ALMO-EDA to include contributions from continuum solvent and application to electro- and photochemical CO2 reduction catalysts.

scholarly journals Consistent Inclusion of Continuum Solvation in Energy Decomposition Analysis: Theory and Application to Molecular CO2 Reduction Catalysts

2020 ◽  
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Kareesa Kron ◽  
Jeffrey Derrick ◽  
Christopher Chang ◽  
...  
Keyword(s):  
Intermolecular Interactions ◽  
Chemical Reactivity ◽  
Decomposition Analysis ◽  
Substituent Effects ◽  
Co2 Reduction ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Coulombic Interaction ◽  
Model Complexes ◽  
Localized Molecular Orbitals

<p>To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to electrochemical CO<sub>2</sub> reduction catalysis. For [FeTPP(CO<sub>2</sub>−κC)]<sup>2−</sup> (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO2 binding, −N(CH<sub>3</sub>)<sub>3</sub><sup>+</sup> (TMA) and −OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The Coulombic interaction between the positively charged TMA group and activated CO<sub>2</sub> is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO<sub>2</sub> via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible “pockets” in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the <i>p</i>-terphenyl radical anion to CO<sub>2</sub> , we demonstrate that the double terminal substitution of <i>p</i>-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.<br></p>

scholarly journals Consistent Inclusion of Continuum Solvation in Energy Decomposition Analysis: Theory and Application to Molecular CO2 Reduction Catalysts

2020 ◽  
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Kareesa Kron ◽  
Jeffrey Derrick ◽  
Christopher Chang ◽  
...  
Keyword(s):  
Intermolecular Interactions ◽  
Chemical Reactivity ◽  
Decomposition Analysis ◽  
Substituent Effects ◽  
Co2 Reduction ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Coulombic Interaction ◽  
Model Complexes ◽  
Localized Molecular Orbitals

<p>To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to electrochemical CO<sub>2</sub> reduction catalysis. For [FeTPP(CO<sub>2</sub>−κC)]<sup>2−</sup> (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO2 binding, −N(CH<sub>3</sub>)<sub>3</sub><sup>+</sup> (TMA) and −OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The Coulombic interaction between the positively charged TMA group and activated CO<sub>2</sub> is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO<sub>2</sub> via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible “pockets” in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the <i>p</i>-terphenyl radical anion to CO<sub>2</sub> , we demonstrate that the double terminal substitution of <i>p</i>-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.<br></p>

scholarly journals Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

2015 ◽  
Vol 11 ◽  
pp. 2727-2736 ◽  
Author(s):  
Diego M Andrada ◽  
Nicole Holzmann ◽  
Thomas Hamadi ◽  
Gernot Frenking
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Heterocyclic Carbenes ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Direct Estimate ◽  
Functional Theory ◽  
Bonding Analysis

Fifteen cyclic and acylic carbenes have been calculated with density functional theory at the BP86/def2-TZVPP level. The strength of the internal X→p(π) π-donation of heteroatoms and carbon which are bonded to the C(II) atom is estimated with the help of NBO calculations and with an energy decomposition analysis. The investigated molecules include N-heterocyclic carbenes (NHCs), the cyclic alkyl(amino)carbene (cAAC), mesoionic carbenes and ylide-stabilized carbenes. The bonding analysis suggests that the carbene centre in cAAC and in diamidocarbene have the weakest X→p(π) π-donation while mesoionic carbenes possess the strongest π-donation.

Characterization of cisplatin/membrane interactions by QM/MM energy decomposition analysis

2021 ◽  
Vol 23 (36) ◽  
pp. 20533-20540
Author(s):  
Gustavo Cárdenas ◽  
Álvaro Pérez-Barcia ◽  
Marcos Mandado ◽  
Juan J. Nogueira
Keyword(s):  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Membrane Interactions

The interactions that control the permeation of cisplatin through a DOPC bilayer are unveiled by a QM/MM EDA scheme.

XEDA , a fast and multipurpose energy decomposition analysis program

2021 ◽  
Author(s):  
Zhen Tang ◽  
Yanlin Song ◽  
Shu Zhang ◽  
Wei Wang ◽  
Yuan Xu ◽  
...  
Keyword(s):  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Analysis Program ◽  
Energy Decomposition
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