Partial Information Decomposition of Electronic Observables Along a Reaction Coordinate
Fuente:
arXiv
Saved in:
| Main Authors: | , |
|---|---|
| Format: | Preprint |
| Published: |
2026
|
| Subjects: | |
| Online Access: | |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866914373078876160 |
|---|---|
| author | Han, Kyunghoon Gallegos, Miguel |
| author_facet | Han, Kyunghoon Gallegos, Miguel |
| contents | A reaction-coordinate--resolved information-theoretic analysis of chemical reactivity is developed using mutual information and partial information decomposition (PID). Along an intrinsic reaction coordinate (IRC), a local empirical distribution is constructed at each position $s$ that couples a coarse-grained geometric progress variable (target) to two electronic readouts (sources), and the joint mutual information $I(T;X,Y)$ is decomposed into redundant, unique, and synergistic contributions using the Williams--Beer PID formalism. In the numerical demonstrations, the target is a binned bond-asymmetry coordinate $ξ=d_{\mathrm{C}\!-\!\mathrm{nuc}}-d_{\mathrm{C}\!-\!\mathrm{LG}}$, while the sources are DDEC6 net atomic charges on the nucleophile and leaving-group centres. Application to three prototypical S$_\mathrm{N}$2 reactions (identity exchange $\mathrm{F^-+CH_3F}$, halide substitution $\mathrm{F^-+CH_3Br}$, and hydroxide substitution $\mathrm{OH^-+CH_3CH_2Br}$) yields compact, symmetry-sensitive signatures of bonding evolution: the identity reaction exhibits mirror-related information profiles with exchange of unique-information contributions between equivalent centres, whereas asymmetric reactions show shifted, centre-specific redistribution among redundancy and synergy as C--X cleavage couples to C--Nu formation. This Supplementary Information provides the formal construction, chemically motivated limiting toy models, a solvable analytic symmetric-transfer model, and the computational protocol used to obtain IRC-resolved PID curves. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2603_05672 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Partial Information Decomposition of Electronic Observables Along a Reaction Coordinate Han, Kyunghoon Gallegos, Miguel Chemical Physics A reaction-coordinate--resolved information-theoretic analysis of chemical reactivity is developed using mutual information and partial information decomposition (PID). Along an intrinsic reaction coordinate (IRC), a local empirical distribution is constructed at each position $s$ that couples a coarse-grained geometric progress variable (target) to two electronic readouts (sources), and the joint mutual information $I(T;X,Y)$ is decomposed into redundant, unique, and synergistic contributions using the Williams--Beer PID formalism. In the numerical demonstrations, the target is a binned bond-asymmetry coordinate $ξ=d_{\mathrm{C}\!-\!\mathrm{nuc}}-d_{\mathrm{C}\!-\!\mathrm{LG}}$, while the sources are DDEC6 net atomic charges on the nucleophile and leaving-group centres. Application to three prototypical S$_\mathrm{N}$2 reactions (identity exchange $\mathrm{F^-+CH_3F}$, halide substitution $\mathrm{F^-+CH_3Br}$, and hydroxide substitution $\mathrm{OH^-+CH_3CH_2Br}$) yields compact, symmetry-sensitive signatures of bonding evolution: the identity reaction exhibits mirror-related information profiles with exchange of unique-information contributions between equivalent centres, whereas asymmetric reactions show shifted, centre-specific redistribution among redundancy and synergy as C--X cleavage couples to C--Nu formation. This Supplementary Information provides the formal construction, chemically motivated limiting toy models, a solvable analytic symmetric-transfer model, and the computational protocol used to obtain IRC-resolved PID curves. |
| title | Partial Information Decomposition of Electronic Observables Along a Reaction Coordinate |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2603.05672 |