On the unusual Stokes shift in the smallest PPE dendrimer building block: Role of the vibronic symmetry on the band origin?

TL;DR

This paper investigates the unusual Stokes shift in PPE dendrimers, proposing that molecular symmetry rules influence spectral behavior beyond the Born-Oppenheimer approximation, supported by quantum dynamics and chemistry simulations.

Contribution

It introduces a novel explanation involving vibronic symmetry effects for the Stokes shift in PPE dendrimers, supported by advanced quantum simulations.

Findings

Vibronic symmetry influences the Stokes shift in PPE dendrimers.

Quantum dynamics simulations support the role of symmetry in spectral features.

The Born-Oppenheimer approximation may not fully describe the system's behavior.

Abstract

1,3-bis(phenylethynyl)benzene is the primary chromophore of light-harvesting polyphenylene ethynylene (PPE) dendrimers. It is experimentally known to share the same absorption spectrum as its pair of diphenylacetylene (aka. tolane) meta-substituted branches, yet exhibits an unusual Stokes shift of about 2000 cm$^{-1}$ with respect to its band origin (corresponding to the loss of one vibrational quantum within the antisymmetric acetylenic stretching) in its emission spectrum. We suggest in the present work the unusual but plausible involvement of molecular symmetry selection rules in a situation where the Born-Oppenheimer approximation is far to be valid. Our hypothesis is comforted with quantum dynamics (MCTDH) simulations of absorption and emission UV-visible spectra based on quantum chemistry (TD-DFT) data and a diabatic vibronic coupling Hamiltonian model.