Article
Chemistry, Physical
Puja Agarwala, Enrique D. Gomez, Scott T. Milner
Summary: This study presents a coarse-graining method for simulating conjugated polymers, allowing for faster and more accurate investigation of their structure and properties. The method is validated through simulations of donor and acceptor polymers, which reveal the influence of interface width and slow cooling on polymer morphology.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Materials Science, Multidisciplinary
D. A. M. Abo-Kahla, M. H. Raddadi, A. -H. Abdel-Aty, M. Abdel-Aty, H. Eleuch
Summary: We investigate the entropy of the donor-acceptor quantum dot system (GaAs - (Ga, Al)As) under the influence of terahertz excitation and magnetic field. The optical Bloch equations of the system are solved considering the total dephasing rate. The analysis reveals the occurrence of sudden death and sudden birth of entropy. It is demonstrated that these phenomena can be controlled by system parameters and the influence of magnetic field on the donor-acceptor system can be determined. By selectively choosing the system's parameters, the dynamics of entropy can be controlled.
RESULTS IN PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Helen Holzel, Philipp Haines, Ramandeep Kaur, Dominik Lungerich, Norbert Jux, Dirk M. Guldi
Summary: Inspired by natural light-induced processes, this study investigates the charge transfer properties and geometric effects of functional materials mimicking photosynthetic reaction centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Materials Science, Multidisciplinary
Maximilian F. X. Dorfner, Sebastian Hutsch, Raffaele Borrelli, Maxim F. Gelin, Frank Ortmann
Summary: In this study, we investigate the charge transfer dynamics of photogenerated excitons at the donor-acceptor interface of an organic solar cell blend under the influence of molecular vibrations. By using an effective Hamiltonian and the matrix-product-state ansatz, we provide insight into different mechanisms of charge separation and their relation to the electronic driving energy.
JOURNAL OF PHYSICS-MATERIALS
(2022)
Article
Chemistry, Physical
Jie Kong, Wei Zhang, Xiaomin Zhang, Bo Liu, Yang Li, Andong Xia
Summary: Understanding the charge transfer/separation processes in donor-pi-acceptor chromophores is important for improving the performance of dye-sensitized solar cells. In this study, two newly synthesized molecules, CS-14 and CS-15, were investigated for their intramolecular charge transfer dynamics. The results showed that the CT/CS characters of the dyes were influenced by solvent polarity. CS-15 exhibited better planarization and slower charge recombination, leading to higher charge migration efficiency in DSSCs.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Anna Kristina Schnack-Petersen, Matyas Papai, Klaus Braagaard Moller
Summary: The photoisomerization reaction of azobenzene in both directions was investigated using the surface hopping procedure with forced jumps based on density functional theory. It was found that the cis to-trans isomerization proceeds stepwise, while the trans-to-cis isomerization occurs in one smooth step. The analysis revealed that two coupled modes must be considered for a fuller picture of the cis to-trans isomerization, while the trans-to-cis isomerization can be well described along only the CNNC dihedral angle. The study provides insights into the interpretation of experimental observations and shows a heavy functional dependency in the structures of the conical intersections (CIs) for both reactive and non-reactive trajectories.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Chemistry, Physical
Courtney A. DelPo, Saeed-Uz-Zaman Khan, Kyu Hyung Park, Bryan Kudisch, Barry P. Rand, Gregory D. Scholes
Summary: Enhanced delocalization is beneficial for absorbing molecules in organic solar cells, and polaritons offer exceptional delocalization that can improve the efficiency of bilayer organic photovoltaics by aiding in exciton delivery to the donor-acceptor interface. The decay of polaritons in bilayer cavities shows an additional pathway through charge transfer, indicating that the charge transfer from the polariton is fast enough to outcompete decay to the ground state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Polymer Science
Justus P. Wesseler, Grant M. Cameron, Peter A. G. Cormack, Nico Bruns
Summary: Polymers with donor-acceptor Stenhouse adducts (DASAs) are important light-responsive materials that can undergo reversible isomerization under visible light. This allows for on-demand property changes in a non-invasive manner. The incorporation of DASAs into crosslinked polymer networks is explored in this study, specifically in styrene-divinylbenzene-based polymer microspheres. The DASA-functionalized microspheres showed significant changes in their properties upon irradiation, making them suitable for applications in various fields.
Article
Chemistry, Physical
Mahabir Prasafd, Niall J. English, Somendra Nath Chakraborty
Summary: The asymmetry of donor-acceptor hydrogen bonds in liquid water is observed through molecular dynamics simulation, with one bond strengthening within donors/acceptors as temperature increases. This asymmetry is present among donors/acceptors but absent in the strongest donor-acceptor pair, highlighting the limitations of using a non-polarisable water model to capture hydrogen bond asymmetry in liquid water.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Physical
Xin Chang, Mohammad Balooch Qarai, Frank C. Spano
Summary: A vibronic exciton model was developed to explain the spectral signatures of HJ-aggregates in oligomers and polymers with donor-acceptor-donor repeat units. The model shows that single chains with enhanced intrachain order exhibit J-behavior, while positive H-promoting interchain Coulomb interactions in aggregates attenuate the vibronic ratio. The ratio formula derived previously for P3HT aggregates was shown to also apply to (DAD)(N) aggregates with slight modifications.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Review
Chemistry, Multidisciplinary
Jinwei Zhao, Junyu Ren, Guang Zhang, Ziqiang Zhao, Shiyong Liu, Wandong Zhang, Long Chen
Summary: Covalent organic frameworks (COFs) with segregated donor-acceptor stacks provide pathways and channels for effective charge carrier transport. Significant progress has been made in the research of D-A COFs over the past decade, focusing on design principles, growing structural diversities, and promising application potentials.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Ulrike Salzner
Summary: The study investigates the unknown properties of Diketopyrrolopyrrole (DPP) homopolymers, suggesting they may have significantly wider conduction bands and n-type conductivity. Comparisons with other unknown donor-acceptor systems show that DPP substitution can reduce bandwidths and decrease electron affinities.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Mikael Unge, Hannes Aspaker, Fritjof Nilsson, Max Pierre, Mikael S. Hedenqvist
Summary: Electrical conductivity of polyethylene is influenced by its semicrystalline structure and morphology. This study presents a model for charge transport simulations in polyethylene, which takes into account the segmentation rules defined through quantum chemistry calculations. The results show that the model can explain the conductivity and activation energy of polyethylene.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Jacob Tinnin, Huseyin Aksu, Zhengqing Tong, Pengzhi Zhang, Eitan Geva, Barry D. Dunietz, Xiang Sun, Margaret S. Cheung
Summary: CTRAMER is an open-source software package for calculating interfacial charge-transfer rate constants in organic photovoltaic materials, based on ab initio calculations and molecular dynamics simulations. The software integrates state-of-the-art tools from different disciplines to study photoinduced charge transfer processes with explicit treatment of the environment, providing tools for investigating other observables of interest.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Simon Dubuis, Angela Dellai, Chloe Courdurie, Josianne Owona, Apostolos Kalafatis, Luc Vellutini, Emilie Genin, Vincent Rodriguez, Frederic Castet
Summary: This study combines HRS experiments and quantum chemical calculations to provide a comprehensive description of the SHG responses of DASAs. The experimental results show that derivatives incorporating a barbituric acid or an indanedione acceptor unit and N-methylaniline donor group exhibit the largest SHG responses. The calculations support the experimental data and reveal the relationship between hyperpolarizabilities, excitation energies, and charge transfer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
A. Coretti, L. Scalfi, C. Bacon, B. Rotenberg, R. Vuilleumier, G. Ciccotti, M. Salanne, S. Bonella
JOURNAL OF CHEMICAL PHYSICS
(2020)
Article
Chemistry, Physical
Antoine Carof, Francois-Xavier Coudert, Dario Corradini, Dominika Lesnicki, Elsa Desmaele, Rodolphe Vuilleumier
Summary: First-principles simulations were used to study the solvation of molecules and ions in molten carbonate electrolysis cells, focusing on CO2 and CO reactions. CO2 was found to form a pyrocarbonate species, while CO could form a stable oxalate species with CO23. O2- was observed to preferentially form a complex with four lithium cations, and CO showed the fastest diffusion among the studied species.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Chemistry, Physical
Laura Scalfi, Benoit Coasne, Benjamin Rotenberg
Summary: The Gibbs-Thomson equation describes the shift of crystallization temperature for a confined fluid with respect to the bulk, but derivations in the literature often rely on nucleation theory arguments or fail to state assumptions clearly. By revisiting derivations, numerical simulations, and experimental comparisons, the application and limitations of this equation can be clarified.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Alessandra Serva, Laura Scalfi, Benjamin Rotenberg, Mathieu Salanne
Summary: Electrochemistry experiments have shown that the capacitance of electrode-electrolyte interfaces is much larger for good metals like gold and platinum compared to carbon-based materials. By adjusting the metallicity of gold through the width of the Gaussian charge distribution, the capacitance of aqueous solutions can be modified. The presence of salt can lead to adsorption of Na+ cations on the surface of metallic gold electrodes.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Giovanni Pireddu, Laura Scalfi, Benjamin Rotenberg
Summary: This study investigates the behavior of a gold electrode interacting with sodium or chloride ions in a vacuum or in water using all-atom constant-potential classical molecular dynamics simulations. The analysis reveals important similarities between the two approaches and highlights limitations of continuum electrostatics, such as neglecting charges induced by adsorbed solvent molecules and screening effects of the solvent. The study also suggests that the conclusions on induced charge density may hold for other ions, solvents, and electrode surfaces.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Iurii Chubak, Laura Scalfi, Antoine Carof, Benjamin Rotenberg
Summary: In this study, the quality of the Sternheimer approximation and the impact of classical force field on the NMR relaxation rates of quadrupolar ions in water were systematically evaluated. The research found that all three types of force fields yield good estimates for smaller and less polarizable solutes when a model-specific Sternheimer parametrization is used. However, polarizable and scaled charge force fields perform better for divalent and more polarizable species.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Multidisciplinary Sciences
Laura Scalfi, Benjamin Rotenberg
Summary: In this study, molecular simulations were used to investigate the effect of the metallic character of solid substrates on solid-liquid interfacial thermodynamics. A thermodynamic integration framework was introduced to compute the evolution of the interfacial free energy, and a simple model was proposed to interpret the evolution of the interfacial free energy. This methodology opens up possibilities for studying the molecular-scale effects of the metallic character of substrates on ionic systems.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Correction
Chemistry, Multidisciplinary
Xiuyun Jiang, Zdenek Futera, Md. Ehesan Ali, Fruzsina Gajdos, Guido F. von Rudorff, Antoine Carof, Marian Breuer, Jochen Blumberger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Samuele Giannini, Wei-Tao Peng, Lorenzo Cupellini, Daniele Padula, Antoine Carof, Jochen Blumberger
Summary: The exciton diffusion in molecular materials is crucial for the performance of organic optoelectronic devices. This study presents a method to propagate excitons through nano-scale materials and reveals a correlation between diffusion constant and quantum delocalization of the exciton. The findings provide insights for improving exciton transport in organic optoelectronic materials.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Philip Loche, Laura Scalfi, Mustakim Ali Amu, Otto Schullian, Douwe J. Bonthuis, Benjamin Rotenberg, Roland R. Netz
Summary: Using classical molecular dynamics simulations, the dielectric properties at interfaces of water with different surfaces (graphene, graphite, hexane, and water vapor) were investigated. It was found that water has an enhanced dielectric response at hydrophobic surfaces. The positions of the dielectric dividing surface vary significantly among the different surfaces, indicating pronounced surface-specific dielectric behavior. The repulsion of ions from the interfaces is dominated by different interactions depending on the surface properties (electrostatic for fluid-fluid interfaces, non-electrostatic for graphene-water interface).
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Alessandro Coretti, Camille Bacon, Roxanne Berthin, Alessandra Serva, Laura Scalfi, Iurii Chubak, Kateryna Goloviznina, Matthieu Haefele, Abel Marin-Lafleche, Benjamin Rotenberg, Sara Bonella, Mathieu Salanne
Summary: Electrochemistry plays a central role in various fields such as biology and energy science, and research involves experimental and theoretical techniques. Modeling and simulation methods like density functional theory and molecular dynamics are essential for understanding the structural and dynamic properties of systems. The polarization effects at the electrode/electrolyte interface are particularly important but difficult to accurately simulate. This study demonstrates how the Ewald summation method incorporates these electrostatic interactions, focusing on the formal setup for calculations with periodic boundary conditions in two dimensions, which differ from the more common three-dimensional case. The implementation is validated on simple systems and a well-known graphite electrode/room-temperature ionic liquid interface, and the capabilities of the software MetalWalls are showcased by studying the adsorption of a complex functionalized electrolyte on a graphite electrode.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Laura Scalfi, Domenico Vitali, Henrik Kiefer, Roland R. Netz
Summary: Finite-size effects pose challenges in molecular dynamics simulations due to their significant impact on computed static and dynamic properties, particularly diffusion constants, friction coefficients, and time- or frequency-dependent response functions. This study investigates the influence of periodic boundary conditions on velocity autocorrelation function and frequency-dependent friction of particles in a fluid, revealing significant effects on long-time behavior starting at the picosecond timescale. An analytical correction is developed to subtract the periodic boundary condition effects, thereby uncovering power-law long-time tails of the memory kernel and velocity autocorrelation function in liquid water and a Lennard-Jones fluid even with small simulation boxes.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Vishal Kumar Porwal, Antoine Carof, Francesca Ingrosso
Summary: The presence of carboxyl groups in a molecule affects its affinity to metal cations and sensitivity to the chemical environment, mainly due to intermolecular hydrogen bonds. Carboxylate groups can also induce intramolecular interactions, impacting the conformational space of biomolecules. To accurately describe these modifications, a compromise between quantum chemical description and explicit solvent molecules is required. This study presents a bottom-up approach combining continuum solvent, microsolvation approach, and QM/MM molecular dynamics simulations to analyze the conformational space and solvation properties of carboxylated (bio)organic anions, providing a detailed description of the solvation shell and intermolecular hydrogen bonds.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Laura Scalfi, Maximilian R. Becker, Roland R. Netz, Marie-Laure Bocquet
Summary: In this study, the authors use spin-polarized ab initio molecular dynamics simulations to compare the aqueous reactivities of iron porphyrin and iron pyridine SACs embedded in graphene, and predict the interfacial water dissociative adsorption mechanism under a moderate electric field for an iron porphyrin SAC.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Physics, Fluids & Plasmas
Cihan Ayaz, Laura Scalfi, Benjamin A. Dalton, Roland R. Netz
Summary: We present a hybrid projection scheme that combines linear Mori projection and conditional Zwanzig projection techniques to derive a generalized Langevin equation (GLE) for a general interacting many-body system. The resulting GLE includes the potential of mean force (PMF) that describes the equilibrium distribution of the system, a random force term that depends on the initial state of the system, and a memory friction contribution. Our hybrid scheme combines desirable properties of Zwanzig and Mori projection schemes. The nonlinear memory friction contribution is related to correlations between the reaction-coordinate velocity and the random force.