A method to capture the large relativistic and solvent effects on the UV-vis spectra of photo-activated metal complexes

Joel Creutzberg*, Erik Donovan Hedegård


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We have recently developed a method based on relativistic time-dependent density functional theory (TD-DFT) that allows the calculation of electronic spectra in solution (Creutzberg, Hedegård, J. Chem. Theory Comput.18, 2022, 3671). This method treats the solvent explicitly with a classical, polarizable embedding (PE) description. Furthermore, it employs the complex polarization propagator (CPP) formalism which allows calculations on complexes with a dense population of electronic states (such complexes are known to be problematic for conventional TD-DFT). Here, we employ this method to investigate both the dynamic and electronic effects of the solvent for the excited electronic states of trans-trans-trans-[Pt(N3)2(OH)2(NH3)2] in aqueous solution. This complex decomposes into species harmful to cancer cells under light irradiation. Thus, understanding its photo-physical properties may lead to a more efficient method to battle cancer. We quantify the effect of the underlying structure and dynamics by classical molecular mechanics simulations, refined with a subsequent DFT or semi-empirical optimization on a cluster. Moreover, we quantify the effect of employing different methods to set up the solvated system, e.g., how sensitive the results are to the method used for the refinement, and how large a solvent shell that is required. The electronic solvent effect is always included through a PE potential.

TidsskriftPhysical Chemistry Chemical Physics
Udgave nummer8
Sider (fra-til)6153-6163
StatusUdgivet - 28. feb. 2023

Bibliografisk note

Funding Information:
E. D. H. thanks The Villum Foundation, Young Investigator Program (grant no. 29412), the Swedish Research Council (grant no. 2019-04205), and the Independent Research Fund Denmark (grants no. 0252-00002B and no. 2064-00002B) for support.

Publisher Copyright:
© 2023 The Royal Society of Chemistry.


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