From Electronic Heterogeneity to Extreme Residence Times: A Multiscale Model of Energetic Stabilization, Stochastic Trapping, and Transport

Persistent local states can arise without a uniform reduction in system-wide mobility.Here, we develop a minimal multiscale model to examine whether mi-croscopic electronic heterogeneity can propagate through energetic stabi-lization into extreme local residence-time statistics.A four-state effective Hamiltonian was used to generate distributionsof coupling-induced stabilization.The uncoupled reference energy was defined consistently with the four-state basis as the minimum energy of the uncoupled states.Electronic heterogeneity systematically broadened the resulting stabi-lization distribution.Across the investigated range, the standard deviation of the stabiliza-tion distribution increased by approximately 1.73-fold.The 99.9th percentile of stabilization increased by approximately 1.67-fold.These energetic distributions were then coupled to a stochastic trap-ping model through an energy-dependent escape probability.Increasing electronic heterogeneity produced a systematic increase inthe upper tail of the residence-time distribution.The ensemble-mean 99.9th percentile of residence time increased byapproximately 1.21-fold.In contrast, the effective diffusion coefficient remained nearly unchanged,with a high-to-low heterogeneity ratio of approximately 0.993.Thus, enhanced extreme local residence did not imply a comparablepopulation-level transport slowdown.To separate effects of mean stabilization from effects of distributionalheterogeneity, the coupled model was compared with a homogeneous mean-matched control.At the highest electronic heterogeneity, the coupled system showed amean increase in the 99.9th-percentile residence time of 2.55 simulationsteps relative to the mean-matched control.A paired bootstrap analysis gave a 95% confidence interval of [1.60, 3.55]for this mean difference.The corresponding mean residence-time ratio was approximately 1.105,with a 95% bootstrap confidence interval of [1.065, 1.145].This residual effect indicates that stabilization heterogeneity can influ-ence extreme residence statistics beyond the effect of mean stabilizationalone.A separate Liouvillian spectral-gap analysis found no evidence for di-rect coupling-induced relaxation slowdown within 10,201 scanned param-eter combinations.These results support a restricted multiscale mechanism in which mi-croscopic electronic heterogeneity broadens an effective stabilization land-scape, which is then transmitted through local escape dynamics and pref-erentially amplified in the extreme tail of residence-time statistics.The framework does not establish a direct mechanism for any specificclimatic, environmental, or biological phenomenon.Rather, it provides a testable theoretical basis for investigating howmicroscopic heterogeneity may contribute to rare, long-lived local statesin more complex nonequilibrium systems.

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Publication Details

Journal
Zenodo (CERN European Organization for Nuclear Research)
Published
2026-10-04
DOI
https://doi.org/10.5281/zenodo.23135474
Primary Topic
Photochemistry and Electron Transfer Studies
Type
preprint
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preprint

From Electronic Heterogeneity to Extreme Residence Times: A Multiscale Model of Energetic Stabilization, Stochastic Trapping, and Transport

Shoko Wakisaka
Zenodo (CERN European Organization for Nuclear Research)
Photochemistry and Electron Transfer Studies
preprint

From Electronic Heterogeneity to Extreme Residence Times: A Multiscale Model of Energetic Stabilization, Stochastic Trapping, and Transport

Shoko Wakisaka
preprint en

Abstract

Persistent local states can arise without a uniform reduction in system-wide mobility.Here, we develop a minimal multiscale model to examine whether mi-croscopic electronic heterogeneity can propagate through energetic stabi-lization into extreme local residence-time statistics.A four-state effective Hamiltonian was used to generate distributionsof coupling-induced stabilization.The uncoupled reference energy was defined consistently with the four-state basis as the minimum energy of the uncoupled states.Electronic heterogeneity systematically broadened the resulting stabi-lization distribution.Across the investigated range, the standard deviation of the stabiliza-tion distribution increased by approximately 1.73-fold.The 99.9th percentile of stabilization increased by approximately 1.67-fold.These energetic distributions were then coupled to a stochastic trap-ping model through an energy-dependent escape probability.Increasing electronic heterogeneity produced a systematic increase inthe upper tail of the residence-time distribution.The ensemble-mean 99.9th percentile of residence time increased byapproximately 1.21-fold.In contrast, the effective diffusion coefficient remained nearly unchanged,with a high-to-low heterogeneity ratio of approximately 0.993.Thus, enhanced extreme local residence did not imply a comparablepopulation-level transport slowdown.To separate effects of mean stabilization from effects of distributionalheterogeneity, the coupled model was compared with a homogeneous mean-matched control.At the highest electronic heterogeneity, the coupled system showed amean increase in the 99.9th-percentile residence time of 2.55 simulationsteps relative to the mean-matched control.A paired bootstrap analysis gave a 95% confidence interval of [1.60, 3.55]for this mean difference.The corresponding mean residence-time ratio was approximately 1.105,with a 95% bootstrap confidence interval of [1.065, 1.145].This residual effect indicates that stabilization heterogeneity can influ-ence extreme residence statistics beyond the effect of mean stabilizationalone.A separate Liouvillian spectral-gap analysis found no evidence for di-rect coupling-induced relaxation slowdown within 10,201 scanned param-eter combinations.These results support a restricted multiscale mechanism in which mi-croscopic electronic heterogeneity broadens an effective stabilization land-scape, which is then transmitted through local escape dynamics and pref-erentially amplified in the extreme tail of residence-time statistics.The framework does not establish a direct mechanism for any specificclimatic, environmental, or biological phenomenon.Rather, it provides a testable theoretical basis for investigating howmicroscopic heterogeneity may contribute to rare, long-lived local statesin more complex nonequilibrium systems.

Zenodo (CERN European Organization for Nuclear Research)
Photochemistry and Electron Transfer Studies
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