Article
Chemistry, Physical
Jakub Kocak, Eli Kraisler, Axel Schild
Summary: When a molecule dissociates, the Kohn-Sham (KS) and Pauli potentials form step structures, critical for describing dissociation and charge-transfer processes. The exact electron factorization (EEF) provides an explanation for these steps, showing they are a result of spatial electron entanglement and charge transfer. Additionally, two methods to reproduce the potentials during dissociation are proposed, offering insights into the encoding of many-electron effects in a one-electron theory.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Materials Science, Multidisciplinary
Salamat Ali, Anand Parkash, Asma A. Alothman, Zainab M. Almarhoon, Mohamed Ouladsmane, Jing Qi
Summary: The advancement of epitaxial technology has allowed for the simulation of oxide heterostructures with unique interfacial material characteristics. This study used density functional theory to explore the possibility of tuning the electron mobility of SrTiO3 through CaSnO3/SrTiO3 and ZnSnO3/SrTiO3 heterostructures. The results showed that the bandgaps of the heterostructure systems were much smaller than bulk STO, indicating the potential for controlling and tuning the bandgap of STO through thin film layer numbers of CSO and ZSO.
ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Kyle R. Bryenton, Adebayo A. Adeleke, Stephen G. Dale, Erin R. Johnson
Summary: This article reviews the history of delocalization error in density-functional theory (DFT), provides conceptual interpretations and illustrative examples of its manifestations, and discusses approaches to reduce this error and its interplay with other shortcomings of popular DFAs.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Leonard C. Pasqualini, Hubert Huppertz, Minyeong Je, Heechae Choi, Jorn Bruns
Summary: Borosulfates, classified as silicate analogue materials, exhibit impressive structural diversity with limited crystallographic data. The compound Sr[B3O(SO4)(4)(SO4H)] is the first borosulfate identified with a triple-vertex linkage of three (BO4) tetrahedra. DFT calculations and experimental studies complement each other to provide insights into the electron distribution and bonding situation within the anionic substructure.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Martin L. Kirk, David A. Shultz, Patrick Hewitt, Ju Chen, Art van der Est
Summary: Photoinduced electron spin polarization (ESP) in the ground state of luminescent materials is investigated, and the phenomenon is found to be influenced by the connecting structure and have a relatively long duration.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Kimihiko Hirao, Takahito Nakajima, Bun Chan
Summary: The study extended Slater's transition state concept to approximate total energy differences using three orbital energies; numerical validation showed accurate reproduction of Delta SCF values; while the current method has some limitations, it contributes to an improved understanding of SCF-type orbital theories.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Materials Science, Multidisciplinary
Sajanthan Sekaran, Masahisa Tsuchiizu, Matthieu Saubanere, Emmanuel Fromager
Summary: Quantum embedding based on reduced density matrices is re-examined using unitary Householder transformations, leading to the development of Ht-DMFET. This method preserves the single-particle character of the bath and produces accurate results for energy matching, particularly in the noninteracting case. Further exploration of connections with density/density matrix functional theories is ongoing.
Article
Chemistry, Physical
Beatriz G. del Rio, Brandon Phan, Rampi Ramprasad
Summary: In this study, a machine learning model is proposed to emulate the essence of density functional theory (DFT) by mapping the atomic structure to the electronic charge density and predicting other properties. This model bypasses the computational cost of solving the central Kohn-Sham equation and maintains chemical accuracy.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Spectroscopy
Debkumar Rana, Arnulf Materny
Summary: This study provides a detailed comparison of optical and electronic properties in organic semiconductor systems under an external electric field using density functional theory. The research enhances understanding of the relationship between chemical structures and optical/electronic properties in organic solar cell systems, and quantitatively extracts the charge-transfer rate influenced by the external electric field by simulating Raman spectra and excited state properties.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Article
Chemistry, Physical
Diptarka Hait, Yu Hsuan Liang, Martin Head-Gordon
Summary: This study explores the prediction of molecular multipole moments and the assessment of performance in describing molecular interactions with external electric fields within density functional theory. The use of translationally invariant second cumulants matrix shows better performance, while some modern functionals may exhibit disappointing results.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Inorganic & Nuclear
M. Sahakyan, V. H. Tran
Summary: The electronic structure of the antiferromagnetic material USn0.5Sb1.5 was investigated using ab-initio calculations. The effects of spin-orbit coupling and Hubbard corrections on the system were considered. It was found that the substitution of Sn led to significant changes in lattice parameters, magnetic moments, and electronic properties. The research provides insights into the behavior of antiferromagnetic materials with Sn substitution.
JOURNAL OF SOLID STATE CHEMISTRY
(2022)
Article
Mathematics, Applied
Bin Gao, Guanghu Hu, Yang Kuang, Xin Liu
Summary: All-electron calculations are crucial in density functional theory, and improving computational efficiency is a challenging task. In this paper, an orthogonalization-free algorithm framework is proposed to solve the nonlinear eigenvalue problem and the total energy minimization problem without invoking orthogonalization in each iteration, thereby enhancing computational efficiency and parallel scalability.
SIAM JOURNAL ON SCIENTIFIC COMPUTING
(2022)
Article
Chemistry, Inorganic & Nuclear
Adilmo F. de Lima
Summary: Spin density functional theory calculations were used to investigate exchange interactions in hexagonal YMnO3 and LuMnO3 multiferroic compounds, with the inclusion of a Hubbard U correction. The intraplane superexchange interaction was found to decrease with increasing U-eff, with the best agreement with experiment found for U-eff values between 2.55 and 4.0 eV. Topological analysis of the electron density indicated an increase in closed-shell interaction of bonds with increasing U-eff. Additionally, both interplane and intraplane super-superexchange interactions were computed and compared with previous studies.
JOURNAL OF SOLID STATE CHEMISTRY
(2021)
Article
Physics, Condensed Matter
Simon Divilov, Wen Wan, Paul Dreher, Emre Bolen, Daniel Sanchez-Portal, Miguel M. Ugeda, Felix Yndurain
Summary: Using spin-resolved density functional theory calculations, the study reveals that the most stable ground state of single-layer NbSe2 is ferrimagnetic, which prevents the development of charge density wave order. The calculated density of states accurately reproduces the experimental electronic and magnetic structure, highlighting the importance of magnetism in understanding the formation mechanisms of 2D superconductivity and CDW order.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2021)
Article
Materials Science, Multidisciplinary
Benjamin X. Shi, Rebecca J. Nicholls, Jonathan R. Yates
Summary: The structure factors obtained from diffraction experiments are crucial for characterizing the electronic and structural properties of materials. In this study, a new approach is proposed to calculate the structure factors by separating the rapidly changing contributions to the electron density and treating them on logarithmic radial grids. The effectiveness of this method is validated by comparing the results with all-electron DFT and experiment.
Article
Physics, Multidisciplinary
M. Herve, V Despre, P. Castellanos Nash, V Loriot, A. Boyer, A. Scognamiglio, G. Karras, R. Bredy, E. Constant, A. G. G. M. Tielens, A. Kuleff, F. Lepine
Summary: The study shows the universal role of correlation bands in ultrafast energy relaxation of size-scalable two-dimensional molecules following ionization by an ultrashort XUV pulse. It observed long lifetimes that nonlinearly increase with the number of valence electrons and proposed a general law based on solid-like electron-phonon scattering. This offers new opportunities in attosecond science and high-energy photophysics.
Article
Physics, Multidisciplinary
Nikolay Golubev, Jiri Vanicek, Alexander Kuleff
Summary: This study reports an extension of the theory underlying attosecond transient absorption spectroscopy for molecules, successfully demonstrated on tracking the electron dynamics oscillations in propiolic acid molecule, and shows that the resolution of ATAS enables tracing electron density dynamics with atomic spatial resolution.
PHYSICAL REVIEW LETTERS
(2021)
Article
Multidisciplinary Sciences
Lorenz S. Cederbaum, Alexander I. Kuleff
Summary: Interatomic Coulombic decay (ICD) is an efficient electronic decay process that occurs in systems embedded in environments. Quantum light has a significant impact on the ICD process, altering it compared to classical ICD, and allowing for control of ICD rates through manipulation of atomic distribution and orientation. In an electromagnetic cavity, the entanglement of atoms can substantially change ICD rates and be utilized to control the process.
NATURE COMMUNICATIONS
(2021)
Article
Physics, Multidisciplinary
Marc Rebholz, Thomas Ding, Victor Despre, Lennart Aufleger, Maximilian Hartmann, Kristina Meyer, Veit Stooss, Alexander Magunia, David Wachs, Paul Birk, Yonghao Mi, Gergana Dimitrova Borisova, Carina da Costa Castanheira, Patrick Rupprecht, Georg Schmid, Kirsten Schnorr, Claus Dieter Schroeter, Robert Moshammer, Zhi-Heng Loh, Andrew R. Attar, Stephen R. Leone, Thomas Gaumnitz, Hans Jakob Woerner, Sebastian Roling, Marco Butz, Helmut Zacharias, Stefan Duesterer, Rolf Treusch, Gunter Brenner, Jonas Vester, Alexander Kuleff, Christian Ott, Thomas Pfeifer
Summary: In this study, an extreme-ultraviolet free-electron laser is used to excite a gas-phase di-iodomethane target, allowing for the investigation of molecular dissociation pathways and geometries in a time-resolved manner. The method presented in this work provides a sensitive approach to study excited-state molecular structures and reactions triggered by core-resonance at specific sites.
Article
Physics, Multidisciplinary
A. Boyer, M. Herve, V Despre, P. Castellanos Nash, V Loriot, A. Marciniak, A. G. G. M. Tielens, A. Kuleff, F. Lepine
Summary: The study reveals that excited cations in PAHs relax through a progressive loss of vibrational selectivity created at the early-stage dynamics, which competes with the recently revealed correlation-band dynamics.
Article
Chemistry, Physical
Jiaqi Zhou, Shaokui Jia, Anna D. Skitnevskaya, Enliang Wang, Theresa Hahnel, Emma K. Grigoricheva, Xiaorui Xue, Jian-Xing Li, Alexander Kuleff, Alexander Dorn, Xueguang Ren
Summary: Hydrogen bonds play a fundamental role in the chemical and physical properties of molecular systems in the condensed phase. However, our understanding of the structural and dynamical properties of hydrogen-bonded complexes in electronic excited states remains very limited.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Physics, Multidisciplinary
Danylo T. Matselyukh, Victor Despre, Nikolay Golubev, Alexander Kuleff, Hans Jakob Woerner
Summary: This study reports the observation of charge migration in neutral silane molecules using X-ray attosecond transient-absorption spectroscopy. The experimental results are supported by quantum-mechanical ab initio calculations, revealing the dynamics and mechanism of this migration phenomenon.
Article
Physics, Multidisciplinary
Diptesh Dey, Alexander I. Kuleff, Graham A. Worth
Summary: The study investigates the creation and dynamical fate of a coherent superposition of electronic states generated in a polyatomic molecule through broadband ionization, as well as the effect of nuclear dynamics on electronic coherence. The key goal of attosecond science is to control electronic motion and design laser control schemes to prolong coherence.
PHYSICAL REVIEW LETTERS
(2022)
Article
Chemistry, Physical
Anna D. Skitnevskaya, Kirill Gokhberg, Alexander B. Trofimov, Emma K. Grigoricheva, Alexander I. Kuleff, Lorenz S. Cederbaum
Summary: After ionization, cation-radicals store internal energy. Auger decay may trigger electron ejection and molecule fragmentation, while intermolecular Coulombic decay and electron-transfer mediated decay prevent fragmentation. The relaxation processes of prototypical heterocycle-water complexes depend on the hydrogen-bonding site, which determines the nature and energetics of involved electronic states. The presence of electron-density donating or accepting neighbor influences the relaxation mechanisms of biologically relevant systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Kalyani Chordiya, Victor Despre, Balazs Nagyilles, Felix Zeller, Zsolt Diveki, Alexander Kuleff, Mousumi Upadhyay Kahaly
Summary: Through the study of overall many-electron dynamics triggered by ionizing the outer-valence orbitals of different tautomers, we observe distinctly different charge dynamics responses among the tautomers. An experimental schematics for detecting and reconstructing such charge dynamics is proposed.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
J. Vester, V. Despre, A. I. Kuleff
Summary: Due to electron correlation, the removal of an electron from a molecule can lead to coherent superposition of cationic states, resulting in pure electronic dynamics in which the ionization-induced hole migrates throughout the system in a short time scale. The coupling to nuclear motion introduces decoherence that traps the charge, and it is important to understand the duration of electronic coherence and the dominant nuclear degrees of freedom responsible for decoherence. Quantum calculations of propynamide reveal that electronic coherences last only 2-3 fs before being destroyed by nuclear motion. Symmetric in-plane modes are primarily responsible for fast electronic decoherence, while other modes have little or no effect on charge migration. This information can guide the development of reduced dimensionality models or the search for molecules with long coherence times.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Anna D. Skitnevskaya, Kirill Gokhberg, Alexander B. Trofimov, Emma K. Grigoricheva, Alexander I. Kuleff, Lorenz S. Cederbaum
Summary: After ionization, cation-radicals of molecules can release internal energy to trigger the ejection of additional electrons, leading to molecule fragmentation. However, intermolecular Coulombic decay (ICD) and electron-transfer mediated decay (ETMD) can prevent fragmentation by causing electrons to be ejected from neighboring molecules. The relaxation processes of imidazole, pyrrole, and pyridine complexes with water are affected by the hydrogen-bonding site of water molecules, which can open or close certain relaxation processes of ionized systems. The presence of electron-density donating or accepting neighbors, such as water or other biomolecules, can strongly affect the relaxation mechanisms of biologically relevant systems with inner-valence vacancies on carbon atoms.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Optics
Victor Despre, Alexander I. Kuleff
Summary: Quantum dynamics calculations show that electron-correlation-driven charge migration in the correlation band of ionized molecules can increase system stability and modify the fragmentation pattern of the molecule. This charge-migration-induced stabilization is a general mechanism that has implications for the development of attochemistry.
Proceedings Paper
Engineering, Electrical & Electronic
D. T. Matselyukh, V Despre, N. Golubev, A. Kuleff, H. J. Woerner
Summary: In this study, the attosecond quantum beat of an electronic state superposition was observed in SiH4 using soft-X-ray attosecond transient-absorption spectroscopy, and its decoherence and revival, induced by non-adiabatic vibrational dynamics, were reproduced using MCTDH calculations.
2021 CONFERENCE ON LASERS AND ELECTRO-OPTICS (CLEO)
(2021)
Proceedings Paper
Engineering, Electrical & Electronic
A. Boyer, M. Herve, V Despre, P. Castellanos Nash, V Loriot, A. Scognamiglio, G. Karras, R. Bredy, E. Constant, A. G. G. M. Tielens, A. Kuleff, F. Lepine
2021 CONFERENCE ON LASERS AND ELECTRO-OPTICS EUROPE & EUROPEAN QUANTUM ELECTRONICS CONFERENCE (CLEO/EUROPE-EQEC)
(2021)