Optical spectra in condensed phases: how the medium polarizability affects charge-transfer dyes

TL;DR

This paper introduces an effective model to analyze how medium polarizability influences the optical spectra of charge-transfer dyes, highlighting differences between antiadiabatic and adiabatic solvation approaches.

Contribution

It presents a novel antiadiabatic model for medium polarizability effects, contrasting it with traditional adiabatic methods in quantum chemical solvation.

Findings

Medium polarizability significantly affects transition frequencies.

The antiadiabatic approach provides different insights compared to adiabatic models.

Medium polarizability influences symmetry-breaking phenomena in dyes.

Abstract

When designing molecular functional materials, the properties of the active specie, the dye, must be optimized fully accounting for environmental effects. Here we present an effective model to account for the spectroscopic effects of the medium electronic polarizability on the properties of charge-transfer dyes. Different classes of molecules are considered and the proposed antiadiabatic approach to solvation is contrasted with the adiabatic approach, currently adopted in all quantum chemical approaches to solvation. Transition frequencies and band-shapes are addressed, and the role of the medium polarizability on symmetry-breaking phenomena is also discussed.