Solvent Effects on Triplet Yields in BODIPY-Based Photosensitizers

TL;DR

This study uses molecular dynamics and quantum theories to understand how solvent polarity influences triplet-state formation in BODIPY-based photosensitizers, emphasizing the role of dielectric stabilization.

Contribution

It introduces detailed molecular models combined with first-principles calculations to analyze solvent effects on triplet yields in organic photosensitizers.

Findings

Triplet yields are highly sensitive to solvent dielectric properties.

Dielectric stabilization of charge transfer intermediates influences triplet formation.

Molecularly detailed models are crucial for understanding excited-state dynamics.

Abstract

We employ molecular dynamics simulations and quantum rate theories to elucidate the complex condensed-phase dynamics underpinning triplet-state formation in organic photosensitizers. Using models informed by first-principles calculations complete with a molecular representation of solvents of different polarities, we elucidate the interplay of the internal and environmental interactions underlying triplet yield. We find that triplet yields depend sensitively on the dielectric stabilization of the charge transfer intermediate that facilitates a transition into the triplet manifold. Our results illustrate the importance of molecularly detailed models in understanding the excited-state internal charge-transfer dynamics of photochemically-relevant organic molecules.