A two-state model of twisted intramolecular chargetransfer in monomethine dyes

TL;DR

This paper introduces a two-state model Hamiltonian to describe how twisting displacements influence charge transfer in monomethine dyes, with implications for understanding environment-dependent fluorescence.

Contribution

It presents a novel, simplified model parameterized by quantum chemical calculations that captures charge transfer behavior and twisting effects in monomethine dyes across different regimes.

Findings

Model describes charge transfer along twisting channels.

Different regimes show distinct polarization and conical intersection behavior.

Selective biasing of twisting channels is limited to near the cyanine limit.

Abstract

A two-state model Hamiltonian is proposed to model the coupling of twisting displacements to charge-transfer behavior in the ground and excited states of a general monomethine dye molecule. This coupling may be relevant to the molecular mechanism of environment-dependent fluorescence yield enhancement. The model is parameterized against quantum chemical calculations on different protonation states of the green fluorescent protein chromophore (GFP), which are chosen to sample different regimes of detuning from the cyanine (resonant) limit. The model provides a simple yet realistic description of the charge transfer character along two possible excited state twisting channels associated with the methine bridge. It describes qualitatively different behavior in three regions that can be classified by their relationship to the resonant (cyanine) limit. The regimes differ by the presence or absence of twist-dependent polarization reversal and the occurrence of conical intersections. We find that selective biasing of one twisting channel over another by an applied diabatic biasing potential can only be achieved in a finite range of parameters near the cyanine limit.