A Quantum Chemical Method for Dissecting London Dispersion Energy into Atomic Building Blocks

London dispersion (LD) forces are ubiquitous in chemistry and biology, governing processes such as binding of drugs to protein targets, the formation and stability of reaction intermediates, and the selectivity of enantioselective transformations. Developing an experimental or quantum chemical method to quantify atomic contributions to LD energy could open up new pathways for controlling reaction selectivity and guiding molecular design. Herein, we initially introduce Atomic Decomposition of London Dispersion energy (ADLD), a computational method that provides atomic-level resolution in quantifying LD energy at the "gold standard" level of quantum chemistry. Through a series of case studies, we reveal that LD is highly sensitive to variations in the electronic structure, including spin state, charge, and valence bond resonance effectskey factors often overlooked. Furthermore, we uncover the fundamental origin of the recently proposed <i>gravitational-like</i> relationship describing the distance dependence of LD energy in molecular systems. In doing so, we reconcile these recent findings with Fritz London's original formulation in 1930, offering a unified perspective on the fundamental nature of LD forces.

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Publication Details

Journal
ACS Central Science
Published
2025-05-08
DOI
https://doi.org/10.1021/acscentsci.5c00356
Citations
6
Primary Topic
Cold Atom Physics and Bose-Einstein Condensates
Type
article
Field-Weighted Citation Impact
7.48

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article

A Quantum Chemical Method for Dissecting London Dispersion Energy into Atomic Building Blocks

Giovanni Bistoni, Lorenzo Baldinelli, Gianluca Regni
6 citations
ACS Central Science
Cold Atom Physics and Bose-Einstein Condensates
7.48
article

A Quantum Chemical Method for Dissecting London Dispersion Energy into Atomic Building Blocks

Giovanni Bistoni, Lorenzo Baldinelli, Gianluca Regni
article en
6 citations

Abstract

London dispersion (LD) forces are ubiquitous in chemistry and biology, governing processes such as binding of drugs to protein targets, the formation and stability of reaction intermediates, and the selectivity of enantioselective transformations. Developing an experimental or quantum chemical method to quantify atomic contributions to LD energy could open up new pathways for controlling reaction selectivity and guiding molecular design. Herein, we initially introduce Atomic Decomposition of London Dispersion energy (ADLD), a computational method that provides atomic-level resolution in quantifying LD energy at the "gold standard" level of quantum chemistry. Through a series of case studies, we reveal that LD is highly sensitive to variations in the electronic structure, including spin state, charge, and valence bond resonance effectskey factors often overlooked. Furthermore, we uncover the fundamental origin of the recently proposed <i>gravitational-like</i> relationship describing the distance dependence of LD energy in molecular systems. In doing so, we reconcile these recent findings with Fritz London's original formulation in 1930, offering a unified perspective on the fundamental nature of LD forces.

ACS Central ScienceVol. 11(6)
University of Perugia (IT)
Università degli Studi di Perugia, Ministero dell'Università e della Ricerca
Sustainable cities and communities
Openalex Percentile: Top 3%
Cold Atom Physics and Bose-Einstein Condensates
7.48
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