2020/01/01 by Joel Creutzberg, Erik D. Hedegård, Erik Donovan Hedegård · 8 citations
Chemistry · Materials Science · Mathematics · Medicine · Physics and Astronomy · #Absorption spectroscopy #Atomic physics #Chemistry #Computational chemistry #Coupling (piping) #Density functional theory #Lanthanide and Transition Metal Complexes #Materials science #Mathematics #Metal complexes synthesis and properties #Molecular physics #Photochemistry and Electron Transfer Studies #Physics #Quantum mechanics #Relativistic quantum chemistry #Scalar (mathematics) #Spectral line #physics.chem-ph
paper · pdf · doi:10.1039/d0cp05143h
published in Physical Chemistry Chemical Physics 22(46), 27013-27023 (Royal Society of Chemistry) · 24 pages, 10 Figures, 1 Table. 25 pages supporting information
openalex publication_date 2020/01/01 · arxiv created 2020/06/29 · arxiv updated 2020/12/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
We report the first systematic investigation of relativistic effects on the UV-vis spectra of two prototype complexes for so-called photo-activated chemotherapy (PACT), trans-trans-trans-[Pt(N3)2(OH)2(NH3)2] and cis-trans-cis-[Pt(N3)2(OH)2(NH3)2]. In PACT, design of new drugs requires in-depth understanding of the photo-activation mechanisms. A first step is usually to rationalize their UV-vis spectra for which time-dependent density functional theory (TD-DFT) is an indispensable tool. We carried out TD-DFT calculations with a systematic series of non-relativistic (NR), scalar-relativistic (SR), and four-component (4c) Hamiltonians. As expected, large differences are found between spectra calculated within 4c and NR frameworks, while the most intense features (found at higher energies below 300 nm) can be reasonably well reproduced within a SR framework. It is also shown that effective core potentials (ECPs) yield essentially similar results as all-electron SR calculations. Yet the underlying transitions can be strongly influenced by spin-orbit coupling, which is only present in the 4c framework: while this can affect both intense and less intense transitions in the spectra, the effect is most pronounced for weaker transitions at lower energies, above 300 nm. Since the investigated complexes are activated with light of wavelengths above 300 nm, employing a method with explicit inclusion of spin-orbit coupling may be crucial to rationalize the activation mechanism.