Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

On the Low-Lying Electronically Excited States of Azobenzene Dimers: Transition Density Matrix Analysis

Version 1 : Received: 18 June 2021 / Approved: 21 June 2021 / Online: 21 June 2021 (10:20:13 CEST)

A peer-reviewed article of this Preprint also exists.

Titov, E. On the Low-Lying Electronically Excited States of Azobenzene Dimers: Transition Density Matrix Analysis. Molecules 2021, 26, 4245. Titov, E. On the Low-Lying Electronically Excited States of Azobenzene Dimers: Transition Density Matrix Analysis. Molecules 2021, 26, 4245.

Journal reference: Molecules 2021, 26, 4245
DOI: 10.3390/molecules26144245

Abstract

Azobenzene-containing molecules may associate with each other in systems such as self-assembled monolayers or micelles. The interaction between azobenzene units leads to a formation of exciton states in these molecular assemblies. Apart from local excitations of monomers, the electronic transitions to the exciton states may involve charge transfer excitations. Here, we perform quantum chemical calculations and apply transition density matrix analysis to quantify local and charge transfer contributions to the lowest electronic transitions in azobenzene dimers of various arrangements. We find that the transitions to the lowest exciton states of the considered dimers are dominated by local excitations, but charge transfer contributions become sizable for some of the lowest ππ* electronic transitions in stacked and slip-stacked dimers at short intermolecular distances. In addition, we assess different ways to partition the transition density matrix between fragments. In particular, we find that the inclusion of the atomic orbital overlap has a pronounced effect on quantifying charge transfer contributions if a large basis set is used.

Subject Areas

azobenzene; transition density matrix; exciton; charge transfer; excited states; TD-DFT; ADC(2)

Comments (0)

We encourage comments and feedback from a broad range of readers. See criteria for comments and our diversity statement.

Leave a public comment
Send a private comment to the author(s)
Views 0
Downloads 0
Comments 0
Metrics 0


×
Alerts
Notify me about updates to this article or when a peer-reviewed version is published.
We use cookies on our website to ensure you get the best experience.
Read more about our cookies here.