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Excited State Tracking During the Relaxation of Coordination Compounds

submitted on 12.12.2018, 14:38 and posted on 12.12.2018, 15:29 by Juan Sanz García, Martial Boggio-Pasqua, Ilaria Ciofini, Marco Campetella
The ability to locate minima on electronic excited states (ESs) potential energy surfaces (PESs) both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic excited states close in energy, but also due to the complex nature of the excited states involved. In this article, we present a simple yet powerful method to follow an excited state of interest during a structural optimization in the case of TMC, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wavefunction overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium-nitrosyl complex which is very problematic with standard approaches.


European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement No 648558 STRIGES CoG grant).


Email Address of Submitting Author


Chimie ParisTech, CNRS



ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no conflict of interest.


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in Journal of Computational Chemistry

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