Article
Chemistry, Multidisciplinary
Lei Wu, Shi-Ya Tang, Shaodong Zhou
Summary: This study benchmarked thirty-seven calculation methods for predicting the homolytic bond dissociation energies of Ag-X complexes, and found that the PBEO/VDZ//omega B97x-D/mVTZ method was the most accurate. Various Ag-X bond energies were estimated, and Hammett-type analysis revealed relationships between BDE values and reactivity parameters for different ligands. Understanding these relationships could provide insights into structure-reactivity correlations in Ag-X-assisted C-H activation/decarboxylation processes.
Article
Chemistry, Inorganic & Nuclear
Shannon E. E. Cooney, Eric Schreiber, William W. W. Brennessel, Ellen M. M. Matson
Summary: Anionic dopants, such as O-atom vacancies, have a significant impact on the thermochemical and kinetic parameters of proton coupled electron transfer (PCET) at metal oxide surfaces. To gain insights, polyoxovanadate-alkoxide clusters are used as models of reducible metal oxide surfaces. The study shows that the presence of O-atom defects weakens the O-H bond strength and enhances the rate of H-atom uptake due to reduced activation barriers for H-atom transfer at the cluster surface.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Physics, Multidisciplinary
S. G. Porsev, M. S. Safronova, M. G. Kozlov
Summary: This study improves the precision of determining nuclear moments by iteratively solving equations for core triple cluster amplitudes in the relativistic coupled-cluster method. Calculations for Th-229(3+) low-lying states were conducted, resulting in nuclear magnetic dipole and electric quadrupole moments with reduced uncertainties. The investigation also touched upon the Bohr-Weisskopf effect and placed constraints on deviations in nuclear magnetization distribution.
PHYSICAL REVIEW LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Gabriele Manca, Fabrizia Fabrizi de Biani, Maddalena Corsini, Cristiana Cesari, Cristina Femoni, Maria Carmela Iapalucci, Stefano Zacchini, Andrea Ienco
Summary: This article provides a detailed analysis of the electronic structure of the pentanuclear bow tie Au/Fe carbonyl cluster [Au{eta(2)-Fe-2(CO)(8)}(2)](-) and questions the traditional assignment of gold in the +3 oxidation state.
INORGANIC CHEMISTRY
(2022)
Article
Optics
Fei-Chen Li, Hao-Xue Qiao, Yong-Bo Tang, Ting-Yun Shi
Summary: In this study, hyperfine-structure constants for the lowest four states of Th-229(3+) were calculated using the relativistic coupled-cluster method. By combining measured data with atomic calculations, magnetic dipole moment and electric quadrupole moment of the Th-229 nucleus were extracted. The analysis showed the importance of nonlinear terms in producing precise values for Th-229 properties.
Article
Chemistry, Inorganic & Nuclear
Matthieu Regnacq, Denis Lesage, Marte S. M. Holmsen, Karinne Miqueu, Didier Bourissou, Yves Gimbert
Summary: The study demonstrates the remarkable catalytic ability of (P,C)-cyclometalated Au(iii) complexes in the intermolecular hydroarylation of alkynes. The previous evidence of an outer-sphere mechanism is confirmed through the analysis of experimental data and DFT calculations. The evaluation of critical energies of dissociation of Au(iii) complexes with different substrates using energy-resolved mass spectrometry experiments and kinetic modeling supports the collisional model and its application to particularly fragile adducts.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Matthieu Regnacq, Denis Lesage, Marte S. M. Holmsen, Karinne Miqueu, Didier Bourissou, Yves Gimbert
Summary: In this study, the mechanism of (P,C)-cyclometalated Au(iii) complexes catalyzing the intermolecular hydroarylation of alkynes is confirmed through experimental data and theoretical calculations, as well as energy-resolved mass spectrometry experiments and kinetic modeling. The results support the previously proposed collisional model and provide insights into the application of this model on fragile adducts.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Bronte J. Charette, Joseph W. Ziller, Alan F. Heyduk
Summary: The nickel(II) complex bearing a protonated redox-active ligand was studied for its ability to serve as a hydrogen atom and hydride donor. The research showed that the complex exists in equilibrium with different coordination states in solution, which correlates with valence tautomerization between the ligand and the nickel center. Additionally, the complex's thermodynamic propensity to participate in ligand-centered H transfer reactions was characterized by bond dissociation free energy and hydricity measurements.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jan Schulz, Reike Clauss, Aleksandr Kazimir, Sieglinde Holzknecht, Evamarie Hey-Hawkins
Summary: The synthesis of B9-Phos ligands with two carboranyl moieties and bulky electron-donating substituents, previously deemed unattainable, is reported. The electrochemical properties of B9-Phos ligands were investigated, showing the ability of mesityl derivatives to form stabilized phosphoniumyl radical cations. The B9-Phos ligands possess a highly electron-releasing character surpassing that of alkyl phosphines and commonly used N-heterocyclic carbenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Jing Tu, Daniele Veclani, Filippo Monti, Andrea Mazzanti, Letizia Sambri, Nicola Armaroli, Andrea Baschieri
Summary: A new synthetic method has been developed for the preparation of unexpected emissive iridium(iii) complexes (A and B). The structures and reaction mechanisms of these complexes were characterized and analyzed. The findings of higher photoluminescence quantum yield in complex A compared to known analogues provide a potential pathway for the direct synthesis of luminescent complexes.
DALTON TRANSACTIONS
(2023)
Article
Multidisciplinary Sciences
Pritam Sadhukhan, Shu-Qi Wu, Shinji Kanegawa, Sheng-Qun Su, Xiaopeng Zhang, Takumi Nakanishi, Jeremy Ian Long, Kaige Gao, Rintaro Shimada, Hajime Okajima, Akira Sakamoto, Joy G. Chiappella, Myron S. Huzan, Thomas Kroll, Dimosthenis Sokaras, Michael L. Baker, Osamu Sato
Summary: Energy harvesting by utilizing optical control has emerged as a promising solution to alleviate energy and environmental crisis. However, it is challenging to realize nano-scale energy storage and conversion in the same material. Here the authors report a nonferroelectric molecular [CoGa] crystal that uses light as an external stimulus to exhibit photoenergy conversion and energy storage properties.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Ahmed M. Abu-Dief, Nouf H. Alotaibi, Eida S. Al-Farraj, Hamza A. Qasem, Seraj Alzahrani, Metwally K. Mahfouz, Aly Abdou
Summary: Coordination compounds of Ag(I), Cu(II), Ni(II), Fe(III), and VO(II) ions were synthesized and their structures were investigated. The ligand formed specific structures with the ions. The structures of the compounds were optimized using density functional theory, and critical theoretical factors were calculated. Furthermore, the biological activities of the compounds were studied using molecular docking and in vitro experiments.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Inorganic & Nuclear
Miguel A. Gonzalvez, Paul Bernhardt, Merce Font-Bardia, Albert Gallen, Jesus Jover, Montserrat Ferrer, Manuel Martinez
Summary: A series of alkali-metal inclusion complexes of a molecular cube have been successfully prepared through a redox-triggered self-assembly process. These complexes are highly stable and soluble in aqueous media, and show inertness to cation exchange while the size of the portal also plays a determining role in the exchange process.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Osvaldo Carreno-Vega, Marlene Vargas-Zamarripa, Pedro Salas, Gonzalo Ramirez-Garcia
Summary: In this study, a new method was developed to sensitively detect salicylic acid (SA) in plant samples by utilizing upconversion nanoparticles decorated with poly(allylamine)-Cu(ii) complex. The method, based on a NIR-activated composite, allows for the determination of SA concentration, providing insights into the activity of SA in plants and contributing to crop yield improvement and food quality assessment.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Gaurav Joshi, Moorkkannur N. Sreerag, Eluvathingal D. Jemmis, John F. Nixon
Summary: The facile ring contraction of [CoCp'(eta(4)-P-4)] and [Ta(CO)(2)Cp(eta(4)-P-4)] induced by m (NHC)-N-Me and the absence of the ring contraction of [FeCp*(eta(5)-P-5)] under the same conditions are studied by density functional theory (DFT) computations. Theoretical approaches involving NBO and IBO analysis provide a qualitative picture of the overall reactions. The role of substituents and the nature of transition metals in determining the energetics of these reactions has also been studied and an isolobal perspective on these systems affords a simplified picture.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Alberto Baiardi, Stephanie A. Grimmel, Miguel Steiner, Paul L. Turtscher, Jan P. Unsleber, Thomas Weymuth, Markus Reiher
Summary: Quantum mechanical methods are crucial for elucidating reaction paths and molecular dynamics. Recent developments cover strategies ranging from heuristic rules based on quantum mechanics, external biases to enforce reactive events, manual steering facilitated by interactive quantum mechanics, to new approaches for transition-state optimization. These explorative approaches are likely to lead to surprising discoveries in computational chemistry by reducing human effort and covering more extensive regions of configuration space.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Katja-Sophia Csizi, Lina Eckert, Christoph Brunken, Thomas B. Hofstetter, Markus Reiher
Summary: In this study, the role of the substrate in the O2 activation process of Rieske dioxygenase was investigated theoretically. The results showed that the presence of substrate did not affect the reaction energies and structural effects at the non-heme FeII center, but played a role in regulating the reactivity of Rieske dioxygenase.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Markus Reiher
Summary: Electronic structure models are essential tools for theoretical studies of chemical phenomena, with importance placed on accuracy, efficiency, and general applicability. The key to future developments lies in providing system-specific uncertainty information for each electronic structure calculation.
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Robin Feldmann, Andrea Muolo, Alberto Baiardi, Markus Reiher
Summary: In this work, we introduce the nuclear-electronic all-particle density matrix renormalization group (NEAP-DMRG) method to solve the molecular Schrodinger equation. By combining it with the nuclear-electronic Hartree-Fock (NEHF-DMRG) approach, we treat nuclei and electrons equally. We demonstrate that orbital entanglement and mutual information can be used as reliable metrics to detect strong correlation effects.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Francesco Bosia, Peikun Zheng, Alain Vaucher, Thomas Weymuth, Pavlo O. Dral, Markus Reiher
Summary: This work discusses the impact of various well-established semi-empirical approximations on calculation speed and their relation to data transfer rates. The study considers desktop computers, local high-performance computing, and remote cloud services to elucidate the effect on interactive calculations for different interfaces.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Robin Feldmann, Alberto Baiardi, Markus Reiher
Summary: This work introduces a generalized framework based on concepts from differential geometry for deriving exact and approximate Newton self-consistent field (SCF) orbital optimization algorithms. Within this framework, the augmented Roothaan-Hall (ARH) algorithm is extended to handle unrestricted electronic and nuclear-electronic calculations. The authors demonstrate that ARH offers a great balance between stability and computational cost for SCF problems that are difficult to converge using conventional first-order optimization strategies. For electronic calculations, ARH overcomes the slow convergence of orbitals in correlated molecules, illustrated by examples of iron-sulfur clusters. For nuclear-electronic calculations, ARH significantly improves convergence even for small molecules, as shown with a series of protonated water clusters.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Review
Chemistry, Multidisciplinary
Katja-Sophia Csizi, Markus Reiher
Summary: Quantum mechanics/molecular mechanics (QM/MM) hybrid models are used to study chemical phenomena in complex molecular environments. While this approach allows for large system sizes at moderate computational costs, constructing the models manually can be tedious. Therefore, developing automated procedures for QM/MM model construction is desired. This article reviews the current state of QM/MM modeling with a focus on automation, covering MM model parametrization, QM region selection, and embedding schemes.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
Review
Biochemistry & Molecular Biology
Alberto Baiardi, Matthias Christandl, Markus Reiher
Summary: Molecular biology and biochemistry interpret microscopic processes in terms of molecular structures and interactions, which are quantum mechanical. However, computational solution of quantum mechanical equations is challenging. Classical mechanics is often used to understand molecular function, mapping electron and nucleus interactions onto classical surrogate potentials. This simplifies computation but ignores quantum correlations. This work discusses how quantum computation can improve simulations of biomolecules, considering both quantum mechanical and classical problems in molecular biology, as well as data-driven approaches of bioinformatics.
Article
Chemistry, Multidisciplinary
Matthew D. Wodrich, Ruben Laplaza, Nicolai Cramer, Markus Reiher, Clemence Corminboeuf
Summary: In this mini review, a computational pipeline developed in the framework of NCCR Catalysis is presented, which can successfully reproduce the enantiomeric ratios of homogeneous catalytic reactions. The pipeline is based on the SCINE Molassembler module, a graph-based software that provides molecular construction algorithms for all periodic table elements. With this pipeline, simultaneous functionalization and generation of ensembles of transition state conformers is possible, allowing exploration of the influence of various substituents on the overall enantiomeric ratio. This provides quick and reliable access to energetically low-lying transition states, which is crucial for in silico catalyst optimization.
Article
Chemistry, Multidisciplinary
Moritz Bensberg, Markus Reiher
Summary: Investigating a reactive chemical system with automated reaction network exploration algorithms allows for a more detailed understanding of the chemical mechanism compared to manual investigation. The proposed algorithm identifies and explores kinetically accessible regions of the reaction network in real-time, providing an unprecedented mechanistic picture. Using the example of the multi-component proline-catalyzed Michael addition reaction, the algorithm demonstrates its ability to uncover intricate details of the reaction mechanism.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Marco Eckhoff, Markus Reiher
Summary: This paper introduces a machine learning potential (MLP) that can maintain high accuracy and requires little computational demand. By introducing element-embracing atom-centered symmetry functions (eeACSFs), MLPs can be trained for each individual system and uncertainty quantification can be used to continually adapt the MLP. Continual learning strategies are proposed to enable autonomous and on-the-fly training on a continuous stream of new data.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Moritz Bensberg, Markus Reiher
Summary: This study demonstrates how active orbital spaces can be consistently selected along reaction coordinates in a fully automated way. The approach combines the Direct Orbital Selection orbital mapping ansatz with the fully automated active space selection algorithm AUTOCAS, without the need for structure interpolation between reactants and products. The algorithm is demonstrated for the potential energy profile of the homolytic carbon-carbon bond dissociation and rotation around the double bond of 1-pentene in the electronic ground state, but it also applies to electronically excited Born-Oppenheimer surfaces.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Robin Feldmann, Alberto Baiardi, Markus Reiher
Summary: In this paper, a symmetry projection technique is presented for enforcing rotational and parity symmetries in nuclear-electronic Hartree-Fock wave functions. A trial wave function with the correct symmetry properties is generated by projecting the wave function onto representations of the three-dimensional rotation group. The efficiency of the technique is demonstrated by calculating the energies of low-lying rotational states of H-2 and H-3(+) molecules.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Enric Petrus, Diego Garay-Ruiz, Markus Reiher, Carles Bo
Summary: In this study, a unique computational approach was used to successfully simulate the self-assembly processes of metal-oxide nanoclusters. By estimating activation energies and correcting pK (a) values, multi-time-scale kinetic simulations were conducted, reproducing reactions ranging from tens of femtoseconds to months of reaction time. Analysis of the kinetic data and reaction network topology revealed the details of the main reaction mechanisms, explaining the origin of kinetic and thermodynamic control. Simulations at alkaline pH fully reproduced experimental evidence as clusters did not form under those conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Robin Feldmann, Alberto Baiardi, Markus Reiher
Summary: We propose a symmetry projection technique for enforcing rotational and parity symmetries in nuclear-electronic Hartree-Fock wave functions, which treats electrons and nuclei equally. By projecting the wave function onto representations of the three-dimensional rotation group, the technique generates a trial wave function with the correct symmetry properties and makes the wave function an eigenfunction of the angular momentum operator.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)