Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Multidisciplinary
Nianjie Liang, Qiaosheng Li, Mengyuan Ge, Defa Gu, Yuzhou Liu
Summary: This study reported a method to synthesize a dimethoxy-terminated siloxane by the ring-opening reaction. The reaction does not require strong acids, strong bases or transition metal catalysts. The structure of the product was confirmed by various analysis techniques and the feasibility of the reaction was proven by computational calculations.
Article
Chemistry, Multidisciplinary
Stefanie Beck, Vanessa Rueck, Lea-Viktoria Pietsch, Christoph Jessen, Andreas J. Kornath
Summary: The reaction of beta-propiolactam in superacidic systems led to the formation of monoprotonated 3-aminopropanoyl fluoride. Diprotonated species beta-alanine was synthesized in the presence of traces of water. Different salts were characterized using low-temperature infrared and Raman spectroscopy, with single-crystal X-ray analyses conducted. Additionally, quantum chemical calculations were carried out to gain a better understanding of the structural properties of protonated beta-propiolactam.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Weihan Rao, Caiyun Cai, Jingyu Tang, Yiman Wei, Caiyun Gao, Lin Yu, Jiandong Ding
Summary: This study investigates the mechanism of ring-opening polymerization of cyclic esters in the presence of stannous octoate through density functional theory calculations, revealing that the carbonyl oxygen plays a significant role and stannous octoate acts as a catalyst rather than an initiator in the process.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yanbang Li, Thomas J. Emge, Antonio Moreno-Vicente, William P. Kopcha, Yue Sun, Iram F. Mansoor, Mark C. Lipke, Gene S. Hall, Josep M. Poblet, Antonio Rodriguez-Fortea, Jianyuan Zhang
Summary: A new multicomponent reaction involving isocyanide, alkynes, and endohedral metallofullerene (EMF) Lu3N@C-80 has been developed to yield metallofulleroids characterized by various analytical techniques. Single crystal studies revealed ordered Lu3N cluster in one ketenimine metallofulleroid, which is rare for EMF monoadducts. Computational analysis confirmed that the motion of the endohedral cluster is influenced by the position of exohedral organic appendants.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Jieun Choi, Taehwan Yu, Hyun-Joon Ha
Summary: The highly strained three-membered aziridine ring was activated as an aziridinium ion through alkylation of the ring nitrogen and subsequent ring opening with external nucleophiles. This method provides an easy route for synthesizing various N-alkylated amine-containing molecules with the introduction of external nucleophiles at either the alpha or beta position.
Article
Chemistry, Multidisciplinary
Wenjuan Yang, Yating Zhu, Junjun Li, Zheng Chen, Farhat Nosheen, Qitao Zhang, Zhicheng Zhang
Summary: The study utilizes heterogeneous non-noble metal iron nanoparticles for catalytic dehydrogenation, demonstrating excellent performance and providing insights into the dehydrogenation mechanism.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Cameron L. Brown, Brandon H. Bowser, Jan Meisner, Tatiana B. Kouznetsova, Stefan Seritan, Todd J. Martinez, Stephen L. Craig
Summary: Woodward and Hoffman once joked about a Maxwell demon that could open a molecule of cyclobutene in a disrotatory fashion. Nearly 40 years later, this concept was realized in the field of covalent polymer mechanochemistry. By combining single-molecule force spectroscopy and computation, the study explored substituent effects in ring-opening reactions of cyclobutene and benzocyclobutene, revealing differences in the forces required for allowed and forbidden reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Stefanie Beck, Christoph Jessen, Andreas J. Kornath
Summary: In binary superacidic systems HF/MF5 (M = Sb, As), transformations of beta-propiolactone were studied at various temperatures. Different salts were obtained depending on the reaction temperature, with monoprotonated products at lower temperatures and cyclic trications at higher temperatures. Protonated species of beta-propiolactone was not observed. The salts were characterized by low temperature Raman and IR spectroscopy, and single-crystal X-ray analyses were performed for selected samples. The formation of acyl cation as a reactive intermediate was proposed based on quantum chemical calculations.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Fabijian Pavosevic, Sharon Hammes-Schiffer, Angel Rubio, Johannes Flick
Summary: This study investigates the possibility of modulating the rate of proton transfer reactions by exploiting the light-matter coupling. The researchers found that by adjusting the polarization direction of the optical cavity, the energy barrier of the proton transfer reaction can be increased or decreased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ida Ritacco, Maria Voccia, Salvatore Impemba, Matteo Farnesi Camellone, Stefano Milione, Lucia Caporaso
Summary: The mechanism of L-lactide polymerization promoted by NSSN zirconium complexes was investigated using DFT methods to understand how the electronic and steric features of the ligand affect the reaction energy. The rate determining step was found to be the opening of the L-lactide ring, and increasing steric hindrance or electron-withdrawing properties of the ligand increased the energy barrier. However, introducing small and electron-releasing substituents on the nitrogen atom of the ligand, such as a methyl group, improved the activity of NSSN zirconium catalysts in the ROP of L-lactide.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Peng-Wei Long, Guoqiang Wang, Hendrik F. T. Klare, Martin Oestreich
Summary: A highly selective cationic rearrangement of beta-silylated cyclopropanes has been reported. The reaction involves deallylation and ring expansion to control the cyclopropane structure and form a quaternary carbon atom.
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
Article
Chemistry, Multidisciplinary
Maria Drosou, Dimitrios A. Pantazis
Summary: The debate over the electronic and geometric structures of the water-oxidizing complex of photosystem II before dioxygen evolution is ongoing. Recent studies have presented contradictory redox formulations for the Mn4CaOx cofactor in the S-3 state, leading to uncertainty about the O-O bond formation in the catalytic cycle. By employing advanced theoretical calculations, researchers were able to evaluate different models for the S-3 state of the oxygen-evolving complex and assess the accuracy of lower-level theoretical approaches.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Spectroscopy
Yi-Wei Fan, Huai-Qian Wang, Hui-Fang Li
Summary: The study on hydrated clusters Co(H2O)(n)(-) in gas phase using DFT coupled with stochastic kicking method reveals that the global minimum structure of Co(H2O)(n)(-) exhibits a low-symmetry pattern. The Co- ion tends to be located at the vertex site of the water molecular clusters to reduce repulsion with O atom. These results demonstrate that the formation of these low-lying isomers is determined by the delicate balance between ion-water and water-water interactions.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Article
Chemistry, Inorganic & Nuclear
Enrico Ravera, Lucia Gigli, Barbara Czarniecki, Lucas Lang, Rainer Kummerle, Giacomo Parigi, Mario Piccioli, Frank Neese, Claudio Luchinat
Summary: Quantum chemical methods for calculating paramagnetic NMR observables are increasingly accessible and are being utilized in inorganic chemistry practice. The study tested the performance of these methods in predicting proton hyperfine shifts of two high-spin pentacoordinate nickel(II) complexes, showing excellent results in challenging the finest level of predictions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Zhigang Ni, Yang Guo, Frank Neese, Wei Li, Shuhua Li
Summary: The paper introduces a cluster-in-molecule (CIM) local correlation approach with an accurate distant pair correlation energy correction, which is crucial for predicting absolute correlation energies and relative energies in large systems. Benchmark calculations demonstrate that the improved CIM approach can recover over 99.94% of the correlation energy calculated by the parent method, providing accurate binding energies for weakly bound complexes of varying sizes.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Bikramjit Sharma, Van Anh Tran, Tim Pongratz, Laura Galazzo, Irina Zhurko, Enrica Bordignon, Stefan M. Kast, Frank Neese, Dominik Marx
Summary: This study aimed to calculate the isotropic hyperfine coupling constant of a pH-sensitive spin probe in a solution using advanced computational techniques and compare it with experimental measurements. The investigation focused on advancing the calculation of EPR parameters in aqueous solutions based on rigorous statistical mechanics and correlated electronic structure techniques. The results showed that computational strategies incorporating explicit water or RISM solvation with DLPNO-CCSD calculations provided accurate predictions for the spin probe's behavior in aqueous solutions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Marvin H. Lechner, Robert Izsak, Marcel Nooijen, Frank Neese
Summary: The variant of the MR-EOMCC method introduces estimated amplitudes from perturbation theory, maintaining many-body formalism and state-universal properties with reduced computational costs. Performance evaluation against reference data on various test sets shows accuracy on par with multireference perturbation theories, especially useful in multistate situations where high precision is not required.
Article
Chemistry, Physical
Lucas Lang, Enrico Ravera, Giacomo Parigi, Claudio Luchinat, Frank Neese
Summary: This study elaborated on the derivation of the correct long-distance limit of pseudo-contact nuclear magnetic resonance chemical shifts from rigorous first-principles quantum mechanics, confirming the classical Kurland-McGarvey theory. The study also discussed the application of the point-dipole approximation (PDA) in approximate density functional theory and Hartree-Fock theories, and demonstrated how it is possible to overcome the previous assumption of a crude effective nuclear charge approximation by using the fully relativistic Dirac equation.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Rami Shafei, Dimitrios Maganas, Philipp Jean Strobel, Peter J. Schmidt, Wolfgang Schnick, Frank Neese
Summary: In this study, a computational protocol is developed to predict the absorption and emission spectral shapes of Eu2+-doped phosphors. The energy distribution and band shape of the emission spectrum are found to be related to the nature of the 4f-5d transitions in the absorption process. Simple descriptors are identified that show a strong correlation with the energy position and bandwidth of the experimental emission bands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Frank Neese
Summary: The latest version 5.0 of the ORCA quantum chemistry program suite represents a significant improvement in performance, numerical robustness, functionality, and user friendliness.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2022)
Article
Chemistry, Physical
Nicolas O. Foglia, Dimitrios Maganas, Frank Neese
Summary: In this work, a time-dependent density functional theory (TD-DFT) scheme for computing optical spectroscopic properties in the framework of linearly and circularly polarized light is presented. The scheme can calculate absorption, circular dichroism, and magnetic circular dichroism spectra, and takes into account relativistic effects and random orientations of molecules.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Robert Izsak, Christoph Riplinger, Nick S. Blunt, Bernardo de Souza, Nicole Holzmann, Ophelia Crawford, Joan Camps, Frank Neese, Patrick Schopf
Summary: Quantum computers are expected to be useful in simulating strongly correlated chemical systems, but careful selection of orbital spaces is crucial. This study presents a scheme for automatically selecting an active space and combines quantum phase estimation and variational quantum eigensolver algorithms to accurately describe the environment. The protocol outlined here can be applied to chemical systems of any size, including those beyond the capabilities of classical computation.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Frank Neese
Summary: This paper describes the SHARK integral generation and digestion engine, which is based on the McMurchie/Davidson approach and utilizes an efficient BLAS algorithm. SHARK can handle various types of basis function integrals and features programming constructs that simplify workflows and avoid code duplication.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Meeting Abstract
Biochemistry & Molecular Biology
Sinjini Bhattacharjee, Frank Neese, Dimitrios A. Pantazis
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2022)
Article
Chemistry, Multidisciplinary
Ingolf Harden, Frank Neese, Giovanni Bistoni
Summary: This study investigates the aggregation process of chiral organocatalysts derived from phosphoric acids using high-level quantum mechanical calculations. The results show that the formation of catalyst dimers is possible and the aggregation process can significantly affect the stereo-controlling factors, reaction kinetics, and selectivity of the transformations.
Article
Chemistry, Multidisciplinary
Ingolf Harden, Frank Neese, Giovanni Bistoni
Summary: The formation of Bronsted acid aggregates in asymmetric organocatalytic reactions has a significant impact on the stereo-controlling factors of the transformations. This study uses high-level quantum mechanical calculations to investigate the influence of catalyst structure and reaction conditions on the spontaneity of the aggregation process, shedding light on its importance.
Article
Chemistry, Physical
M. Atanasov, N. Spiller, F. Neese
Summary: This study uses first principles calculations to simulate magnetic and spectroscopic data, providing an explanation for the stability of a mixed valence binuclear transition metal complex. The study also proposes a new model to interpret the magnetic behavior of the complex.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
