How Dispersion Interactions at the Excited State Can Tune Photochromism of Embedded Chromophores
Ciro A. Guido, Lorenzo Cupellini, Benedetta Mennucci, Carles Curutchet
TL;DR
This paper introduces a new computational method to study how dispersion forces affect the behavior of chromophores in excited states.
Contribution
The novel QM/MMPol-cLR3 framework incorporates state-specific dispersion for accurate excited-state simulations.
Findings
Dispersion interactions control excited-state solvatochromism through two distinct mechanisms.
In azulene, dispersion causes opposite shifts of La and Lb states due to polarizability changes.
Application to the LH2 complex shows pigment-dependent dispersion shifts affecting energy transfer.
Abstract
We present QM/MMPol-cLR3, a polarizable embedding quantum mechanics/molecular mechanics (QM/MM) framework that includes explicit, state-specific dispersion terms. This method enables a rigorous treatment of dispersion on top of electrostatic and induction effects in ground- and excited-state calculations. Using QM/MMPol-cLR3, we show that dispersion interactions control excited-state solvatochromism through two distinct mechanisms. In azulene, opposite shifts of the La and Lb states arise from state-specific dispersion linked to changes in excited-state polarizability. In bacteriochlorophyll a, dispersion instead stems from the interplay between polarizability changes and transition-dipole-driven response, governing the Q y and Q x shifts. Finally, application to the LH2 complex reveals pigment-dependent dispersion shifts between the B800 and B850 rings, impacting the…
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Taxonomy
TopicsPhotochromic and Fluorescence Chemistry · Light effects on plants · Spectroscopy and Quantum Chemical Studies