Smooth Things Come in Threes: A Diabatic Surrogate Model for Conical Intersection Optimization

The optimization of conical intersection structures is complicated by the nondifferentiability of the adiabatic potential energy surfaces. In this work, we build a pseudodiabatic surrogate model, based on Gaussian process regression, formed by three smooth and differentiable surfaces that can adequa...

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Veröffentlicht in:Journal of chemical theory and computation 2023-06, Vol.19 (11), p.3418-3427
Hauptverfasser: Fdez. Galván, Ignacio, Lindh, Roland
Format: Artikel
Sprache:eng
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Zusammenfassung:The optimization of conical intersection structures is complicated by the nondifferentiability of the adiabatic potential energy surfaces. In this work, we build a pseudodiabatic surrogate model, based on Gaussian process regression, formed by three smooth and differentiable surfaces that can adequately reproduce the adiabatic surfaces. Using this model with the restricted variance optimization method results in a notable decrease of the overall computational effort required to obtain minimum energy crossing points.
ISSN:1549-9618
1549-9626
1549-9626
DOI:10.1021/acs.jctc.3c00389