Intermolecular Interactions through Energy Decomposition: A Chemist’s Perspective

2016 ◽  
pp. 350-381
Keyword(s):  
Intermolecular Interactions ◽  
Energy Decomposition

Energy decomposition of intermolecular interactions in energetic co-crystals

CrystEngComm ◽  
2017 ◽  
Vol 19 (19) ◽  
pp. 2687-2694 ◽  
Author(s):  
Qun Zeng ◽  
Yu Ma ◽  
Jinshan Li ◽  
Chaoyang Zhang
Keyword(s):  
Intermolecular Interactions ◽  
Energy Decomposition

scholarly journals Energy, orbital and structural stacking landscape of a purine homodimer system

2020 ◽  
Vol 139 (10) ◽  
Author(s):  
Tomasz Sierański
Keyword(s):  
Potential Energy ◽  
Intermolecular Interactions ◽  
Potential Energy Surfaces ◽  
Natural Bond Orbital ◽  
Natural Bond Orbital Analysis ◽  
Energy Sources ◽  
Energy Decomposition ◽  
Energy Surfaces ◽  
Orbital Analysis ◽  
Insight Into

Abstract The multidimensional study, combining the extensive calculations of potential energy surfaces for the parallel-displaced configurations and methods such as energy decomposition and natural bond orbital analysis, has been carried out. The resulted data give an energy, orbital and structural landscapes of this biologically essential system. The balance of the two energy sources, electrostatic and dispersion, is clearly visible. The obtained results, taken as a whole, provide an insight into the hierarchy of intermolecular interactions in the purine system, together with their sources.

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>

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