Polarizable embedding complex polarization propagator in four- and two-component frameworks

Joel Creutzberg*, Erik D. Hedegård

*Kontaktforfatter for dette arbejde

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Abstrakt

Explicit embedding methods combined with the complex polarization propagator (CPP) enable the modeling of spectroscopy for increasingly complex systems with a high density of states. We present the first derivation and implementation of the CPP in four- and exact-two-component (X2C) polarizable embedding (PE) frameworks. We denote the developed methods PE-4c-CPP and PE-X2C-CPP, respectively. We illustrate the methods by estimating the solvent effect on ultraviolet-visible (UV-vis) and X-ray atomic absorption (XAS) spectra of [Rh(H2O)6]3+ and [Ir(H2O)6]3+ immersed in aqueous solution. We moreover estimate solvent effects on UV-vis spectra of a platinum complex that can be photochemically activated (in water) to kill cancer cells. Our results clearly show that the inclusion of the environment is required: UV-vis and (to a lesser degree) XAS spectra can become qualitatively different from vacuum calculations. Comparison of PE-4c-CPP and PE-X2C-CPP methods shows that X2C essentially reproduces the solvent effect obtained with the 4c methods.

OriginalsprogEngelsk
TidsskriftJournal of Chemical theory and Computation
Vol/bind18
Udgave nummer6
Sider (fra-til)3671-3686
ISSN1549-9618
DOI
StatusUdgivet - 14. jun. 2022

Bibliografisk note

Funding Information:
The authors thank The Villum Foundation, Young Investigator Program (grant no. 29412), the Swedish Research Council (grant no. 2019-04205), and Independent Research Fund Denmark (grant no. 0252-00002B) for support. The computations were performed on computer resources provided by the Swedish National Infrastructure for Computing (SNIC) at Lunarc (Lund University) and HPC2N (Umeå University).

Publisher Copyright:
© 2022 American Chemical Society.

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