A method to capture the large relativistic and solvent effects on the UV-vis spectra of photo-activated metal complexes
(2023) In Physical Chemistry Chemical Physics 25(8). p.6153-6163- Abstract
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... (More)
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.
(Less)
- author
- Creutzberg, Joel LU and Hedegård, Erik Donovan LU
- organization
- publishing date
- 2023
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Physical Chemistry Chemical Physics
- volume
- 25
- issue
- 8
- pages
- 11 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:85148422700
- pmid:36752122
- ISSN
- 1463-9076
- DOI
- 10.1039/d2cp04937f
- language
- English
- LU publication?
- yes
- id
- 18cdf656-fe39-49cd-a6a7-453fce9a7e2c
- date added to LUP
- 2023-03-07 15:01:19
- date last changed
- 2024-04-17 18:21:43
@article{18cdf656-fe39-49cd-a6a7-453fce9a7e2c,
abstract = {{<p>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(N<sub>3</sub>)<sub>2</sub>(OH)<sub>2</sub>(NH<sub>3</sub>)<sub>2</sub>] 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.</p>}},
author = {{Creutzberg, Joel and Hedegård, Erik Donovan}},
issn = {{1463-9076}},
language = {{eng}},
number = {{8}},
pages = {{6153--6163}},
publisher = {{Royal Society of Chemistry}},
series = {{Physical Chemistry Chemical Physics}},
title = {{A method to capture the large relativistic and solvent effects on the UV-vis spectra of photo-activated metal complexes}},
url = {{http://dx.doi.org/10.1039/d2cp04937f}},
doi = {{10.1039/d2cp04937f}},
volume = {{25}},
year = {{2023}},
}