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Path-dependency of energy decomposition analysis & the elusive nature of bonding.

ABSTRACT: Here, we provide evidence of the path-dependency of the energy components of the energy decomposition analysis scheme, EDA, by studying a set of thirty-one closed-shell model systems with the D_2h symmetry point group. For each system, we computed EDA components from nine different pathways and numerically showed that the relative magnitudes of the components differ substantially from one path to the other. Not surprisingly, yet unfortunately, the most significant variations in the relative magnitudes of the EDA components appear in the case of species with bonds within the grey zone of covalency and ionicity. We further discussed that the role of anions and their effect on arbitrary Pauli repulsion energy components affects the nature of bonding defined by EDA. The outcome variation by the selected partitioning scheme of EDA might bring arbitrariness when a careful comparison is overlooked.

SUBMITTER: Poater J

PROVIDER: S-EPMC8790740 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Path-dependency of energy decomposition analysis & the elusive nature of bonding.

Poater Jordi J Andrada Diego M DM Solà Miquel M Foroutan-Nejad Cina C

Physical chemistry chemical physics : PCCP 20220126 4

Here, we provide evidence of the path-dependency of the energy components of the energy decomposition analysis scheme, EDA, by studying a set of thirty-one closed-shell model systems with the <i>D</i><sub>2h</sub> symmetry point group. For each system, we computed EDA components from nine different pathways and numerically showed that the relative magnitudes of the components differ substantially from one path to the other. Not surprisingly, yet unfortunately, the most significant variations in ...[more]

PMID: 35018916

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Project description:Lithium amides are versatile C-H metallation reagents with vast industrial demand because of their high basicity combined with their weak nucleophilicity, and they are applied in kilotons worldwide annually. The nuclearity of lithium amides, however, modifies and steers reactivity, region- and stereo-selectivity and product diversification in organic syntheses. In this regard, it is vital to understand Li-N bonding as it causes the aggregation of lithium amides to form cubes or ladders from the polar Li-N covalent metal amide bond along the ring stacking and laddering principle. Deaggregation, however, is more governed by the Li←N donor bond to form amine adducts. The geometry of the solid state structures already suggests that there is σ- and π-contribution to the covalent bond. To quantify the mutual influence, we investigated [{(Me2NCH2)2(C4H2N)}Li]2 (1) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA). This new approach allows for the grading of electrostatic Li+N-, covalent Li-N and donating Li←N bonding, and provides a way to modify traditional widely-used heuristic concepts such as the -I and +I inductive effects. The electron density ρ(r) and its second derivative, the Laplacian ∇2ρ(r), mirror the various types of bonding. Most remarkably, from the topological descriptors, there is no clear separation of the lithium amide bonds from the lithium amine donor bonds. The computed natural partial charges for lithium are only +0.58, indicating an optimal density supply from the four nitrogen atoms, while the Wiberg bond orders of about 0.14 au suggest very weak bonding. The interaction energy between the two pincer molecules, (C4H2N)22-, with the Li22+ moiety is very strong (ca. -628 kcal mol-1), followed by the bond dissociation energy (-420.9 kcal mol-1). Partitioning the interaction energy into the Pauli (ΔEPauli), dispersion (ΔEdisp), electrostatic (ΔEelstat) and orbital (ΔEorb) terms gives a 71-72% ionic and 25-26% covalent character of the Li-N bond, different to the old dichotomy of 95 to 5%. In this regard, there is much more potential to steer the reactivity with various substituents and donor solvents than has been anticipated so far.

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Path-dependency of energy decomposition analysis & the elusive nature of bonding.

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Path-dependency of energy decomposition analysis & the elusive nature of bonding.

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