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Kozdra, M., Brandell, D., Araujo, M. & Mace, A. (2024). The sensitive aspects of modelling polymer-ceramic composite solid-state electrolytes using molecular dynamics simulations. Physical Chemistry, Chemical Physics - PCCP, 26(7), 6216-6227
Open this publication in new window or tab >>The sensitive aspects of modelling polymer-ceramic composite solid-state electrolytes using molecular dynamics simulations
2024 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 26, no 7, p. 6216-6227Article in journal (Refereed) Published
Abstract [en]

Solid-state composite electrolytes have arisen as one of the most promising materials classes for next-generation Li-ion battery technology. These composites mix ceramic and solid-polymer ion conductors with the aim of combining the advantages of each material. The ion-transport mechanisms within such materials, however, remain elusive. This knowledge gap can to a large part be attributed to difficulties in studying processes at the ceramic-polymer interface, which are expected to play a major role in the overall ion transport through the electrolyte. Computational efforts have the potential of providing significant insight into these processes. One of the main challenges to overcome is then to understand how a sufficiently robust model can be constructed in order to provide reliable results. To this end, a series of molecular dynamics simulations are here carried out with a variation of certain structural (surface termination and polymer length) and pair potential (van der Waals parameters and partial charges) models of the Li7La3Zr2O12 (LLZO) poly(ethylene oxide) (PEO) system, in order to test how sensitive the outcome is to each variation. The study shows that the static and dynamic properties of Li-ion are significantly affected by van der Waals parameters as well as the surface terminations, while the thickness of the interfacial region - where the structure-dynamic properties are different as compared to the bulk-like regime - is the same irrespective of the simulation setup. 

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2024
Keywords
Ethylene; Ions; Lanthanum compounds; Lithium compounds; Lithium-ion batteries; Polyethylene oxides; Solid electrolytes; Solid-State Batteries; Van der Waals forces; Zirconium compounds; Ceramic polymers; Composite electrolytes; Composite solids; Dynamics properties; Dynamics simulation; Polymer ceramic composite; Solid state composites; Solid-state electrolyte; Surface termination; Van der Waal; Molecular dynamics
National Category
Materials Chemistry Physical Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-98638 (URN)10.1039/d3cp04617f (DOI)001155316100001 ()38305339 (PubMedID)2-s2.0-85184003729 (Scopus ID)
Funder
Swedish Research Council, 2019-05366, 2020-05223Swedish Energy Agency, 50098-1
Available from: 2024-02-27 Created: 2024-02-27 Last updated: 2024-02-27Bibliographically approved
Zhang, C., Cheng, J., Chen, Y., Chan, M. K. Y., Cai, Q., Carvalho, R. P., . . . Sundararaman, R. (2023). 2023 Roadmap on molecular modelling of electrochemical energy materials. Journal of Physics: Energy, 5(4), Article ID 041501.
Open this publication in new window or tab >>2023 Roadmap on molecular modelling of electrochemical energy materials
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2023 (English)In: Journal of Physics: Energy, E-ISSN 2515-7655, Vol. 5, no 4, article id 041501Article, review/survey (Refereed) Published
Abstract [en]

New materials for electrochemical energy storage and conversion are the key to the electrification and sustainable development of our modern societies. Molecular modelling based on the principles of quantum mechanics and statistical mechanics as well as empowered by machine learning techniques can help us to understand, control and design electrochemical energy materials at atomistic precision. Therefore, this roadmap, which is a collection of authoritative opinions, serves as a gateway for both the experts and the beginners to have a quick overview of the current status and corresponding challenges in molecular modelling of electrochemical energy materials for batteries, supercapacitors, CO2 reduction reaction, and fuel cell applications.

Place, publisher, year, edition, pages
Institute of Physics Publishing (IOPP), 2023
Keywords
electrochemical interfaces, density-functional theory, molecular dynamics simulation, electrochemical energy storage, machine learning, electrocatalysis
National Category
Energy Engineering
Research subject
Materials Science
Identifiers
urn:nbn:se:kau:diva-97389 (URN)10.1088/2515-7655/acfe9b (DOI)001090149100001 ()2-s2.0-85177181901 (Scopus ID)
Funder
Swedish Energy Agency, P50638-1EU, Horizon 2020, 771294, 851441, 957189, 949012VinnovaKnut and Alice Wallenberg FoundationAcademy of Finland, 338228
Available from: 2023-11-16 Created: 2023-11-16 Last updated: 2023-12-04Bibliographically approved
Carvalho, R. P., Brandell, D. & Araujo, M. (2023). An evolutionary-driven AI model discovering redox-stable organic electrode materials for alkali-ion batteries. Energy Storage Materials, 61, Article ID 102865.
Open this publication in new window or tab >>An evolutionary-driven AI model discovering redox-stable organic electrode materials for alkali-ion batteries
2023 (English)In: Energy Storage Materials, ISSN 2405-8289, E-ISSN 2405-8297, Vol. 61, article id 102865Article in journal (Refereed) Published
Abstract [en]

Data-driven approaches have been revolutionizing materials science and materials discovery in the past years. Especially when coupled with other computational physics methods, they can be applied in complex high-throughput schemes to discover novel materials, e.g. for batteries. In this direction, the present work provides a robust AI-driven framework, to accelerate the discovery of novel organic-based materials for Li-, Na- and K-ion batteries. This platform is able to predict the open-circuit voltage of the respective battery and provide an initial assessment of the materials redox stability. The model was employed to screen 45 million small molecules in the search for novel high-potential cathodes, resulting in a proposed shortlist of 3202, 689 and 702 novel compounds for Li-, Na- and K-ion batteries, respectively, considering only the redox stable candidates. 

Place, publisher, year, edition, pages
Elsevier, 2023
Keywords
Batteries, Artificial intelligence, Organic electrode, High-voltage cathode material, Redox stability
National Category
Materials Chemistry Physical Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-96415 (URN)10.1016/j.ensm.2023.102865 (DOI)001053590000001 ()2-s2.0-85166955764 (Scopus ID)
Funder
Swedish Research Council, 2018-04506, 2020-05223Swedish Energy Agency, 45420-1Linköpings universitet
Available from: 2023-08-21 Created: 2023-08-21 Last updated: 2023-09-11Bibliographically approved
Jalan, I., Marchiori, C., Genene, Z., Johansson, A., Araujo, M., Wang, E., . . . Moons, E. (2023). Donor-acceptor polymer complex formation in solution confirmed by spectroscopy and atomic-scale modelling. Journal of Materials Chemistry C, 11(27), 9316-9326
Open this publication in new window or tab >>Donor-acceptor polymer complex formation in solution confirmed by spectroscopy and atomic-scale modelling
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2023 (English)In: Journal of Materials Chemistry C, ISSN 2050-7526, E-ISSN 2050-7534, Vol. 11, no 27, p. 9316-9326Article in journal (Refereed) Published
Abstract [en]

In all-polymer solar cells, high performance is attributed to the fine-grained morphology of the film in the active layer. However, the mechanism by which this fine-grained morphology is achieved remains unknown. Polymeric non-fullerene acceptors have the potential to restrict the self-aggregation, typical of non-fullerene small molecule acceptors. Here we employed a blend of the polymeric acceptor PF5-Y5 and the donor polymer PBDB-T to investigate the balance between molecular interactions in solution. Temperature-dependent absorption spectra show evidence of temperature-induced disaggregation of both donor and acceptor polymers, where the donor polymer disaggregation depends on the solvent polarity. Concentration-dependent fluorescence spectra of blend solutions display blue-shifted acceptor emission upon dilution, similar to that observed in acceptor solutions, and a decreased tendency for charge transfer from donor to acceptor upon dilution. Excitation spectra of dilute blend solutions contain an increased contribution to the long-wavelength acceptor emission, as compared to pure acceptor solutions, from a chromophore that absorbs in a region where the donor does not absorb. These observations can be explained by donor-acceptor complexation in dilute blend solutions, that is stabilized in more polar solvents. Moreover, the near IR-region of the absorption spectrum could be matched with the calculated electronic excitations of donor-acceptor complexes of PBDB-T and PF5-Y5 oligomers. The results corroborate that the interaction between segments of the donor and acceptor polymer chains favours the formation of donor-acceptor charge transfer complexes, stabilized by hybridization of the molecular orbitals, which reduces the electronic energy. The proposed donor-acceptor complex formation competes with the donor and acceptor self-aggregation and is influenced by the solvent environment. These pre-formed donor-acceptor complexes in low-concentration solutions can be expected to have important consequences on the film morphology of all-polymer blends. The results from this joint experimental-theoretical spectroscopy study provide insights that can guide the design of compatible donor and acceptor polymers for future high-performance organic solar cells.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2023
National Category
Polymer Chemistry Theoretical Chemistry
Research subject
Chemistry; Materials Science
Identifiers
urn:nbn:se:kau:diva-94224 (URN)10.1039/d1tc03853b (DOI)001019691000001 ()2-s2.0-85164140693 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation, 2016.0059Swedish Energy Agency, 48598-1Swedish National Space Board, 174/19 and 137/21Swedish Research Council, 2014-05984
Note

This paper was included as a manuscript in Ishita Jalan's PhD thesis entitled "Solution Chemistry and Morphological Properties for Organic Solar Cells: Exploring Alternative Solvents Using Microgravity and Modelling as Tools", 2023:13.

Available from: 2023-04-10 Created: 2023-04-10 Last updated: 2023-08-09Bibliographically approved
Khan, Z., Martinelli, A., Franco, L. R., Kumar, D., Idström, A., Evenäs, L., . . . Crispin, X. (2023). Mass Transport in “Water-in-Polymer Salt” Electrolytes. Chemistry of Materials, 35, 6382-6395
Open this publication in new window or tab >>Mass Transport in “Water-in-Polymer Salt” Electrolytes
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2023 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 35, p. 6382-6395Article in journal (Refereed) Published
Abstract [en]

“Water-in-polymer salt” electrolytes (WiPSEs) based on potassium polyacrylate (PAAK) belong to a new family of “water-in-salt” electrolytes that is envisioned as a potential solution for large-scale supercapacitors to balance the electric grid at short time scales. The WiPSEs display a broad electrochemical stability window up to 3 V, yet they are nonflammable and provide high ionic conductivity (100 mS/cm) as required in high-power devices. However, the transport of matter in PAAK-based WiPSEs has not been studied. In this work, we have extensively characterized PAAK by spectroscopic methods such as Raman spectroscopy and NMR diffusometry to determine the state of water and elucidate the mechanism of ionic transport as well as its interplay with water and polymer chain dynamics, which reveals that a significant proportion of the transport in WiPSEs is attributed to hydrated cations. The results are further supported by molecular dynamics (MD) simulations. Finally, the potential of WiPSEs based on PAAK is demonstrated in an activated carbon-based supercapacitor operating up to 2 V with reasonable self-discharge. This proof of concept shows promise for low-cost and large-scale supercapacitors.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2023
Keywords
Activated carbon, Display devices, Electric discharges, Electrolytes, Electrolytic capacitors, Molecular dynamics, Spectroscopic analysis, American Chemical Society, Electric grids, Electrochemical stabilities, High-power devices, Large-scales, Non-flammable, Polymer salts, Salt electrolytes, Short time scale, Spectroscopic method, Supercapacitor
National Category
Physical Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-96498 (URN)10.1021/acs.chemmater.3c01089 (DOI)001040465300001 ()2-s2.0-85167801328 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation, 2009-00971, KAW 2020.0174Swedish Research Council, 2020-05223Swedish Energy Agency, P52023-1ÅForsk (Ångpanneföreningen's Foundation for Research and Development), 21-130, 22-134
Available from: 2023-08-29 Created: 2023-08-29 Last updated: 2023-09-04Bibliographically approved
Wu, J., Ling, Z., Franco, L. R., Jeong, S. Y., Genene, Z., Mena, J., . . . Wang, E. (2023). On the Conformation of Dimeric Acceptors and Their Polymer Solar Cells with Efficiency over 18 %. Angewandte Chemie International Edition
Open this publication in new window or tab >>On the Conformation of Dimeric Acceptors and Their Polymer Solar Cells with Efficiency over 18 %
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2023 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773Article in journal (Refereed) Published
Abstract [en]

The determination of molecular conformations of oligomeric acceptors (OAs) and their impact on molecular packing are crucial for understanding the photovoltaic performance of their resulting polymer solar cells (PSCs) but have not been well studied yet. Herein, we synthesized two dimeric acceptor materials, DIBP3F-Se and DIBP3F-S, which bridged two segments of Y6-derivatives by selenophene and thiophene, respectively. Theoretical simulation and experimental 1D and 2D NMR spectroscopic studies prove that both dimers exhibit O-shaped conformations other than S- or U-shaped counter-ones. Notably, this O-shaped conformation is likely governed by a distinctive "conformational lock" mechanism, arising from the intensified intramolecular & pi;-& pi; interactions among their two terminal groups within the dimers. PSCs based on DIBP3F-Se deliver a maximum efficiency of 18.09 %, outperforming DIBP3F-S-based cells (16.11 %) and ranking among the highest efficiencies for OA-based PSCs. This work demonstrates a facile method to obtain OA conformations and highlights the potential of dimeric acceptors for high-performance PSCs.

Place, publisher, year, edition, pages
John Wiley & Sons, 2023
Keywords
Acceptor, Molecular Conformation, Oligomer, Selenophene, Solar Cells
National Category
Organic Chemistry Biophysics
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-96239 (URN)10.1002/anie.202302888 (DOI)001030527700001 ()37380618 (PubMedID)2-s2.0-85165198230 (Scopus ID)
Funder
Swedish Research Council, 2016-06146; 2019-04683; 2020-05233Swedish Research Council Formas, 2017.0186Knut and Alice Wallenberg Foundation, 2016.0059Swedish Energy Agency, P2021-90067
Available from: 2023-08-08 Created: 2023-08-08 Last updated: 2023-08-09Bibliographically approved
Prasad, S., Marchiori, C., Genene, Z., Ericsson, L., Araujo, M., Wang, E. & Moons, E. (2023). Photostability of Y-type electron acceptor molecules and related copolymer. In: Gang Li, Natalie Stingelin, Ana Flávia Nogueira, Thuc-Quyen Nguyen, Ellen Moons, Barry P. Rand (Ed.), Proceedings Volume 12660, Organic, Hybrid, and Perovskite Photovoltaics XXIV;: . Paper presented at SPIE Optics + Photonics, San Diego, United States, August 20-24, 2023.. SPIE - The International Society for Optics and Photonics, 12660
Open this publication in new window or tab >>Photostability of Y-type electron acceptor molecules and related copolymer
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2023 (English)In: Proceedings Volume 12660, Organic, Hybrid, and Perovskite Photovoltaics XXIV; / [ed] Gang Li, Natalie Stingelin, Ana Flávia Nogueira, Thuc-Quyen Nguyen, Ellen Moons, Barry P. Rand, SPIE - The International Society for Optics and Photonics, 2023, Vol. 12660Conference paper, Published paper (Refereed)
Abstract [en]

The lifetime of organic solar cells critically depends on the photochemical stability of the materials. To shed light on the photostability of novel Y-series electron acceptors, we investigate the evolution of optical properties and composition during one-sun illumination in ambient atmosphere of thin films of the small-molecule acceptor Y5 and its copolymers PF5-Y5 and PYT. We employ UV-vis, Fourier-transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS), to assess changes in these properties as a function of illumination time. UV-Vis spectra show that PF5-Y5 undergoes rapid photobleaching, while the Y5 spectrum remains essentially unaffected even after 30 hours of exposure. The absorption spectrum of PYT, which contains a different co-mer than PF5-Y5, is only weakly affected. XPS C1s spectra of the PF5- Y5 film show a decreasing main peak and the development of a new component after 30 hours exposure, while the Y5 film surface composition remained intact. The photodegradation products of PF5-Y5 are characterized by the presence of new carbonyl groups, emerging as absorption bands in the FTIR spectra, while such spectral changes are absent for the Y5 film, indicating that Y5 is resistant to photooxidation, while PF5-Y5 undergoes photochemical reactions. The faster photodegradation of PF5-Y5 compared to Y5 and PYT raises the question about the role of the copolymer’s BDT moiety in the photooxidation. These new insights on the dependence of the photostability of acceptor molecules on their molecular structure are expected to contribute to the design of stable acceptor copolymers for organic solar cells with long operational lifetimes. 

Place, publisher, year, edition, pages
SPIE - The International Society for Optics and Photonics, 2023
Keywords
co-polymer, non-fullerene acceptor, organic photovoltaics, photooxidation
National Category
Other Physics Topics
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-97578 (URN)10.1117/12.2679517 (DOI)2-s2.0-85176501822 (Scopus ID)
Conference
SPIE Optics + Photonics, San Diego, United States, August 20-24, 2023.
Available from: 2023-11-30 Created: 2023-11-30 Last updated: 2023-11-30Bibliographically approved
Sousa, O. M., Sorgenfrei, F., Assali, L. V., Lalic, M. V., Klautau, A. B., Thunström, P., . . . Petrilli, H. M. (2023). Pressure effect on the structural, electronic, and magnetic properties of the battery cathode material LiMn2O4: An ab-initio study. Journal of Physics and Chemistry of Solids, 175, Article ID 111198.
Open this publication in new window or tab >>Pressure effect on the structural, electronic, and magnetic properties of the battery cathode material LiMn2O4: An ab-initio study
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2023 (English)In: Journal of Physics and Chemistry of Solids, ISSN 0022-3697, E-ISSN 1879-2553, Vol. 175, article id 111198Article in journal (Refereed) Published
Abstract [en]

LiMn2O4 is a battery cathode material with desirable properties such as low cost, low toxicity, high natural abundance of Mn, and environmental compatibility. By means of first-principles calculations, we study the structural, magnetic, and electronic properties of LiMn2O4 under ambient conditions and high hydrostatic pressures (until 20 GPa). We obtain two oxidation states for Mn, even using a cubic structure, which differ in all analyzed properties: structural, electronic, and magnetic. At P > 0, such properties were found to display a standard behavior decreasing smoothly and linearly with pressure. Furthermore, the enthalpy of cubic and orthorhombic structures under low and high-pressure conditions were examined, showing that no cubic to orthorhombic phase transition exists in all the investigated pressure range, nor is a magnetic cubic to a non-magnetic cubic phase transition possible.

Place, publisher, year, edition, pages
Elsevier, 2023
Keywords
Cathodes, Electronic properties, Electronic structure, Hydrostatic pressure, Lithium compounds, Pressure effects, Structural properties, Ab initio study, Cathodes material, Cubic structure, Electronic and magnetic properties, Electronic.structure, Limn2O4 under pressure, Low toxicity, Low-costs, Natural abundance, Property, Manganese compounds
National Category
Condensed Matter Physics
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-93592 (URN)10.1016/j.jpcs.2022.111198 (DOI)000923161400001 ()2-s2.0-85146264323 (Scopus ID)
Funder
Swedish Foundation for Strategic ResearchKnut and Alice Wallenberg FoundationEU, European Research CouncilSwedish Research CouncilSwedish Energy Agency
Available from: 2023-02-13 Created: 2023-02-13 Last updated: 2023-03-23Bibliographically approved
Zaar, F., Araujo, M., Emanuelsson, R., Stromme, M. & Sjodin, M. (2023). Tetraphenylporphyrin electrocatalysts for the hydrogen evolution reaction: applicability of molecular volcano plots to experimental operating conditions. Dalton Transactions, 52(30), 10348-10362
Open this publication in new window or tab >>Tetraphenylporphyrin electrocatalysts for the hydrogen evolution reaction: applicability of molecular volcano plots to experimental operating conditions
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2023 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 52, no 30, p. 10348-10362Article in journal (Refereed) Published
Abstract [en]

Recent years have seen an increasing interest in molecular electrocatalysts for the hydrogen evolution reaction (HER). Efficient hydrogen evolution would play an important role in a sustainable fuel economy, and molecular systems could serve as highly specific and tunable alternatives to traditional noble metal surface catalysts. However, molecular catalysts are currently mostly used in homogeneous setups, where quantitative evaluation of catalytic activity is non-standardized and cumbersome, in particular for multistep, multielectron processes. The molecular design community would therefore be well served by a straightforward model for prediction and comparison of the efficiency of molecular catalysts. Recent developments in this area include attempts at applying the Sabatier principle and the volcano plot concept - popular tools for comparing metal surface catalysts - to molecular catalysis. In this work, we evaluate the predictive power of these tools in the context of experimental operating conditions, by applying them to a series of tetraphenylporphyrins employed as molecular electrocatalysts of the HER. We show that the binding energy of H and the redox chemistry of the porphyrins depend solely on the electron withdrawing ability of the central metal ion, and that the thermodynamics of the catalytic cycle follow a simple linear free energy relation. We also find that the catalytic efficiency of the porphyrins is almost exclusively determined by reaction kinetics and therefore cannot be explained by thermodynamics alone. We conclude that the Sabatier principle, linear free energy relations and molecular volcano plots are insufficient tools for predicting and comparing activity of molecular catalysts, and that experimentally useful information of catalytic performance can still only be obtained through detailed knowledge of the catalytic pathway for each individual system.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2023
National Category
Physical Chemistry Organic Chemistry Theoretical Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-96242 (URN)10.1039/d3dt01250f (DOI)001030623300001 ()37462421 (PubMedID)2-s2.0-85166191165 (Scopus ID)
Funder
Swedish Research Council Formas, 2019-01285ÅForsk (Ångpanneföreningen's Foundation for Research and Development), 19-352Swedish Research Council, 2018-05973; 2020-05233Swedish Energy Agency, 45420-1
Available from: 2023-08-08 Created: 2023-08-08 Last updated: 2023-08-11Bibliographically approved
Franco, L. R., Toledo, K. C., Matias, T. A., Araujo, M., Araki, K. & Coutinho, K. (2023). Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution. Physical Chemistry, Chemical Physics - PCCP, 25(36), 24475-24494
Open this publication in new window or tab >>Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution
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2023 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 25, no 36, p. 24475-24494Article in journal (Refereed) Published
Abstract [en]

Mononuclear polypyridine ruthenium (Ru) complexes can catalyze various reactions, including water splitting, and can also serve as photosensitizers in solar cells. Despite recent progress in their synthesis, accurately modeling their physicochemical properties, particularly in solution, remains challenging. Herein, we conduct a theoretical investigation of the structural and electronic properties of a mononuclear Ru-aqua polypyridine complex in aqueous solution, considering five of its possible oxidation/protonation states species: [RuII(H2O)(py)(bpy)2]2+, [RuII(OH)(py)(bpy)2]+, [RuIII(H2O)(py)(bpy)2]3+, [RuIII(OH)(py)(bpy)2]2+ and [RuIV(O)(py)(bpy)2]2+, where py = pyridine and bpy = 2,2 & PRIME;-bipyridine. At first, we investigate the impact of proton-coupled and non-coupled electron transfer reactions on the geometry and electronic structure of the complexes in vacuum and in solution, using an implicit solvent model. Then, using a sequential multiscale approach that combines quantum mechanics and molecular mechanics (S-QM/MM), we examine the explicit solvent effects on the electronic excitations of the complexes, and compare them with the experimental results. The complexes were synthesized, and their absorption spectra measured in aqueous solution. To accurately describe the QM interactions between the metal center and the aqueous ligand in the MM simulations, we developed new force field parameters for the Ru atom. We analyze the solvent structure around the complexes and account for its explicit influence on the polarization and electronic excitations of the complexes. Notably, accounting for the explicit solvent polarization effects of the first solvation shells is essential to correctly describe the energy of the electronic transitions, and the explicit treatment of the hydrogen bonds at the QM level in the excitation calculations improves the accuracy of the description of the metal-to-ligand charge-transfer bands. Transition density matrix analysis is used to characterize all electronic transitions in the visible and ultraviolet ranges according to their charge-transfer (CT) character. This study elucidates the electronic structure of those ruthenium polypyridyl complexes in aqueous solution and underscores the importance of precisely describing solvent effects, which can be achieved employing the S-QM/MM method. Ru-aqua complex in water, showcasing Ru atom, coordinated water, and hydrogen bonds on left; UV-Vis spectrum and comparison to experiment on right. QM/MM approach emphasized.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2023
National Category
Physical Chemistry Inorganic Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-96715 (URN)10.1039/D3CP02154H (DOI)001056504200001 ()2-s2.0-85170532020 (Scopus ID)
Available from: 2023-09-15 Created: 2023-09-15 Last updated: 2023-11-02Bibliographically approved
Projects
Atomistic Modeling of Advanced Materials for CO2 Reduction: A Promising Approach for Conversion and Storage of Solar Energy [2012-06186_VR]; Uppsala UniversityAdvanced Nanostructured Materials for Efficient PEM fuel cells [2013-06655_VR]; Uppsala UniversityAdvanced Hybrid Materials for High-Energy Density Storage: Fundamentals and Design [2014-05984_VR]; Uppsala UniversityOrganiska Elektrodmaterial med Hög Kapacitet för Gröna Batterier [P45420-1_Energi]; Uppsala University
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0001-5192-0016

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