Accurate Electronic and Optical Properties of Organic Doublet Radicals Using Machine Learned Range-Separated Functionals

11 April 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Luminescent organic semiconducting doublet-spin radicals are unique and emergent optical materials because their fluorescent quantum yields (Φfl) are not compromised by spin-flipping intersystem crossing (ISC) into any dark high-spin states. The multi-configurational nature of radical electronic structures challenges computational studies in the framework of single-reference density functional theory (DFT) and introduces room for method improvement. In the present study, we extended our earlier development of a machine-learned range-separated hybrid functional, referred to as ML-ωPBE, from closed-shell molecules to doublet-spin radicals, and assessed its performance for the original training set of 3,926 organic semiconducting molecules and an external test set of 64 organic semiconducting radicals from five categories. Interestingly, for this external test set, ML-ωPBE reproduced the optimal value of ω, the molecule-dependent range-separation parameter, from the first-principles OT-ωPBE functional with a small mean absolute error (MAE) of 0.0197 a0−1 and with a significant save of computational cost by 2.46 orders of magnitude. This result demonstrated excellent generalizability and transferability of ML-ωPBE among a variety of organic semiconducting species. To further assess the predictive power of ML-ωPBE on organic semiconducting radicals, we also compared its performance on experimentally measurable absorption and fluorescence energies (Eabs’s and Efl’s), evaluated using time-dependent DFT (TDDFT), with nine conventional functionals. ML-ωPBE reproduced experimental Eabs’s and Efl’s for most radicals in questions, with small MAEs of 0.222 and 0.121 eV, marginally worse from OT-ωPBE. Our work not only illustrated a successful extension of stacked ensemble machine learning (SEML) framework from closed-shell molecules to open-shell doublet-spin radicals, but also opened the venue for the calculations of optical properties these using single-reference TDDFT.

Keywords

density functional theory
exchange-correlation functional
range-separated hybrid
machine learning
stacked ensemble generalization
organic semiconducting radicals
optical properties

Supplementary materials

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Supporting Information: Accurate Electronic and Optical Properties of Organic Doublet Radicals Using Machine Learned Range-Separated Functionals
Description
Details of quantum chemical calculations; brief revisit of the SEML model; similarity and difference in chemical space between singlet molecules and doublet radicals; error statistics of ML-ωPBE and other XC functionals in optical properties; and configurations of frontier MOs and NTOs (PDF).
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Molecular Geometries in XYZ Coordinates
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Optimized D0 and D1 geometries for all radicals in the external test set.
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SMILES Strings and Range Separation Parameters
Description
SMILES strings and ω values for all radicals in the external test set.
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Supplementary weblinks

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