Valence-bond Non-equilibrium Solvation Model for a Twisting Monomethine Cyanine

TL;DR

This paper introduces a two-state valence-bond model to analyze how non-equilibrium solvation influences the excited-state twisting and fluorescence behavior of monomethine cyanines, highlighting the role of TICT states and solvation effects.

Contribution

It presents a novel valence-bond model that predicts multiple twisting pathways and the influence of solvation on conical intersections in monomethine cyanines.

Findings

Multiple low-energy twisting channels exist in the excited state.

Solvation can stabilize different TICT states, affecting fluorescence.

Conical intersection seams expand with increasing solvent polarity.

Abstract

We propose and analyze a two-state valence-bond model of non-equilibrium solvation effects on the excited-state twisting reaction of monomethine cyanines. Suppression of this reaction is thought responsible for environment-dependent fluorescence yield enhancement in these dyes. Fluorescence is quenched because twisting is accompanied via the formation of dark twisted intramolecular charge-transfer (TICT) states. For monomethine cyanines, where the ground state is a superposition of structures with different bond and charge localization, there are two possible twisting pathways with different charge localization in the excited state. For parameters corresponding to symmetric monomethines, the model predicts two low-energy twisting channels on the excited-state surface that lead to a manifold of twisted intramolecular charge-transfer (TICT) states. For typical monomethines, twisting on the excited state surface will occur with a small barrier or no barrier. Changes in the solvation configuration can differentially stabilize TICT states in channels corresponding to different bonds, and that the position of a conical intersection between adiabatic states moves in response to solvation to stabilize either one channel or the other. There is a conical intersection seam that grows along the bottom of the excited-state potential with increasing solvent polarity. For monomethine cyanines with modest-sized terminal groups in moderately polar solution, the bottom of the excited-state potential surface is completely spanned by a conical intersection seam.