Article
Chemistry, Physical
Adam Rettig, Martin Head-Gordon, Srinivas Doddipatla, Zhenghai Yang, Ralf Kaiser
Summary: The gas-phase preparation of ethynylsilylene through single-collision conditions has been studied, showing a barrierless reaction pathway and the formation of a distinct intermediate. The system of dicarbon-silane serves as a benchmark to explore the consequence of a single collision, leading to the formation of a nonclassical silacarbene.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Roberto Cammi, Bo Chen
Summary: In this study, we propose a new theory for investigating the potential energy surface of compressed molecular systems. By using a Legendre transform, we derive an analytical expression for the gradient of the total energy, which can be used for optimizing the geometries of compressed molecular systems. Additionally, we demonstrate that the potential energy surface can be explicitly studied as a function of pressure, and it is connected to the well-known Hammond postulate.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Dirk Bakowies
Summary: ATOMIC is a thermochemistry protocol that evaluates atomization energies and enthalpies of formation using bond separation reactions. ATOMIC-2 is an improved version that increases computational efficiency, accuracy, and adds an error and uncertainty model.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Inorganic & Nuclear
Xueying Guo, Tilong Yang, Yichi Zhang, Fu Kit Sheong, Zhenyang Lin
Summary: Despite the long history of research in transition metal (TM) complexes, the study of TM-aluminyl complexes is still in its early stage of development. This work uses density functional theory calculations to explore the reactivity of a series of TM-aluminyl complexes towards heteroallenes, providing insights into the nucleophilicity of the TM-Al σ-bond.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Joseph P. Heindel, Sotiris S. Xantheas
Summary: The study provides a detailed analysis of the many-body expansion (MBE) for alkali metal and halide ion-water interactions, highlighting the significance of 2-B ion-water interactions in the total cluster binding energy and the impact of different ions on the neighboring hydrogen bonded water network. The results also reveal a linear anticorrelation between ion-water and water-water interactions, indicating a disruption and alteration in the neighboring water network strength by the presence of various ions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Jozsef Csoka, Mihaly Kallay
Summary: Several approaches to improve the efficiency of Hartree-Fock and Kohn-Sham self-consistent field calculations have been introduced, utilizing a simple first-order energy correction. The new methods show speedups of up to 80% with minimal loss of accuracy, making them promising for practical applications.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Daniel Witsch, Eileen Doering, Alexander A. Breier, Jurgen Gauss, Thomas F. Giesen, Guido W. Fuchs
Summary: In this study, dialuminum monoxide (Al2O) was produced by laser ablation of an aluminum target with the addition of nitrous oxide. The molecule was cooled in a supersonic beam expansion, allowing for the measurement of ro-vibrational transitions. Experimental results were supported by quantum-chemical calculations, confirming the accuracy of the derived molecular parameters.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Vincenzo Barone, Luigi Crisci, Silvia Di Grande
Summary: A new strategy for computationally studying medium-sized molecules in the gas phase is proposed in this paper, which performs better than existing model chemistries without the need for empirical parameters. The method allows nonspecialists to accurately study medium- to large-sized molecules at a reasonable cost using standard electronic structure codes.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Xiang Yuan, Lucas Visscher, Andre Severo Pereira Gomes
Summary: This paper presents the implementation of a module for generating natural orbitals (NOs) for correlated wavefunctions, particularly the second order Moller-Plesset perturbation frozen natural orbitals (MP2FNOs), as part of a novel implementation of relativistic coupled cluster theory. The study finds that MP2FNOs accelerate the convergence of correlation energy uniformly across the Periodic Table and reliable estimates for energy and molecular properties can be obtained by truncating the virtual molecular orbital spaces to about half their original size.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Augustin Bussy, Jurg Hutter
Summary: The study discusses the implementation of linear-response time-dependent density functional theory for core level near-edge absorption spectroscopy. The method is validated and shown to be efficient, with the ability to accurately describe spin-orbit coupling effects. The study also demonstrates the scalability of the method for extended systems and the potential for speedups through GPU utilization.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Multidisciplinary Sciences
Patrick Vossnacker, Alisa Wuest, Thomas Keilhack, Carsten Muller, Simon Steinhauer, Helmut Beckers, Sivathmeehan Yogendra, Yuliya Schiesser, Rainer Weber, Marc Reimann, Robert Mueller, Martin Kaupp, Sebastian Riedel
Summary: Chloride ions have been found to be efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Through control experiments, the role of [NEt3Me][Cl-3] as an active species has been highlighted. This discovery opens up the possibility of using [NEt3Me]Cl as a catalyst for phosgene production and chlorine storage.
Article
Chemistry, Physical
Emily E. Claveau, Evangelos Miliordos
Summary: This study investigates the electronic structure of MO2+ diatomic species with M = Ti-Cu using multi-reference electronic structure calculations combined with large basis sets. The systems show high efficiency in activating the C-H of saturated hydrocarbons. Different transition metals are divided into three groups based on their electronic states, providing insights into the reactivity and stability of MO2+ units. The reported spectroscopic constants will aid future experimental investigations, and periodic trends for bond lengths, energetics, excitation energies, and wavefunction composition are discussed in detail, showing the high accuracy of the quintuple-zeta basis sets.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Soren Holm, Pablo A. Unzueta, Keiran Thompson, Todd J. Martinez
Summary: In this study, a graph neural network model is developed and trained to correct the basis set incompleteness error between a small and large basis set at the RHF and B3LYP levels of theory. The results show that fitting an ML model to correct the BSIE is better at generalizing to systems not seen during training compared to fitting to the total potential. Acceptable performance is achieved when the training data sufficiently resemble the systems one wants to make predictions on.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Astronomy & Astrophysics
Vincent J. Esposito, Tarek Trabelsi, Joseph S. Francisco
Summary: New spectroscopic parameters have been calculated to aid in the detection of several molecules in laboratory and observational settings. The rotational frequencies and vibrational spectra are discussed for different temperature conditions. Deuteration is found to affect the vibrational frequency, providing a potential confirmation method. Additionally, the electronic absorption spectra of aluminum and magnesium compounds are predicted to have distinct features.
ASTROPHYSICAL JOURNAL
(2022)
Article
Astronomy & Astrophysics
Tarek Trabelsi, Vincent J. Esposito, Joseph S. Francisco
Summary: Accurate vibrational frequencies, rotational constants, and vertical transition energy were obtained for AlNH2 and HAlNH isomers using ab initio calculations. These isomers are potential candidates for astronomical observation. AlNH2 and HAlNH are thermodynamically stable with predicted dissociation energies of 4.39 and 3.60 eV, respectively. The anharmonic frequencies and spectroscopic constants reported for these isomers can facilitate their experimental differentiation. The absorption spectra of AlNH2 and HAlNH were also evaluated, showing strong absorption around specific wavelengths.
ASTROPHYSICAL JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
E. Albanese, M. Corno, M. Baricco, B. Civalleri
Summary: Modeling thin films of beta-Ca(BH4)(2) reveals that nanostructuration of the material can significantly decrease dehydrogenation enthalpy. Quantum mechanical calculations show that reducing the size from bulk to nanoscale leads to a notable decrease in decomposition enthalpy, supporting the potential advantages of nanostructured metal borohydrides for energy storage applications.
RESEARCH ON CHEMICAL INTERMEDIATES
(2021)
Article
Chemistry, Physical
Alicia Schuitemaker, Paolo Raiteri, Raffaella Demichelis
Summary: Classical molecular and lattice dynamics were used to investigate the structure and dynamics of water on various surfaces of vaterite. Three stable surfaces were identified, showing minimal structural changes in contact with water and resistance to dissolution. The study provides important insights into the surface chemistry of vaterite and its potential role in biomineralization.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Physics, Multidisciplinary
Jacques K. Desmarais, Alessandro Erba, Yuanming Pan, Bartolomeo Civalleri, John S. Tse
Summary: The pressure-induced isostructural electronic phase transitions in EuO were studied using global-hybrid density functional theory, revealing an insulator-to-metal transition at 12 GPa and a second transition at 30-35 GPa associated with changes in the occupation of Eu d orbitals. The abrupt depopulation of e(g) symmetry orbitals along the Eu-O direction was identified as a means to alleviate electron-electron repulsion in the highly compressed structures.
PHYSICAL REVIEW LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Julie Aufort, Alicia Schuitemaker, Rebecca Green, Raffaella Demichelis, Paolo Raiteri, Julian D. Gale
Summary: In this study, the adsorption of small molecules with two different organic functional groups on the surface of calcite at the interface with aqueous solution was investigated using free energy methods. Polarizability was taken into account and the results showed that including polarization provided a more consistent description with experimental observations, especially at calcite steps.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Physical
Lorenzo Dona, Jan Gerit Brandenburg, Bartolomeo Civalleri
Summary: The chemical versatility and modular nature of Metal-Organic Frameworks (MOFs) make them unique hybrid inorganic-organic materials for several important applications. The recently proposed sol-3c methods, which combine hybrid functionals and basis set superposition error corrections, have been successfully used to model the structural, vibrational, electronic, and adsorption properties of large MOFs with reasonable computing resources.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Vanessa Schoeppler, Phil K. Cook, Carsten Detlefs, Raffaella Demichelis, Igor Zlotnikov
Summary: Biomineralized structures are complex functional hierarchical assemblies composed of biomineral building blocks joined together by an organic phase. In this study, the newly developed synchrotron-based dark-field X-ray microscopy method is employed to study the link between 3D crystallographic properties of relatively large calcitic prisms in the shell of the mollusc Pinna nobilis and their local lattice properties with extremely high angular resolution down to 0.001 degrees.
ADVANCED MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Annika F. Moslein, Lorenzo Dona, Bartolomeo Civalleri, Jin-Chong Tan
Summary: This study directly investigates local defects in ZIF-8 nano- and microcrystals using near-field IR nanospectroscopy and density functional theory calculations. The research shows that some structural defects gradually disappear during crystallization, while dangling and missing linker defects persist. These structural defects reduce the Young's modulus of the crystals but also offer opportunities for defect engineering to tune the performance of ZIF-8 by providing additional adsorption sites.
ACS APPLIED NANO MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Paolo Cleto Bruzzese, Enrico Salvadori, Bartolomeo Civalleri, Stefan Jaeger, Martin Hartmann, Andreas Poeppl, Mario Chiesa
Summary: By using EPR and HYSCORE spectroscopies along with ab initio calculations, we have determined the structure of framework-bound monomeric hydroxo-Cu-II in copper-loaded chabazite. The complex forms three coordinating bonds with zeolite lattice oxygens and interacts with the cage through hydrogen bonding.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Nanoscience & Nanotechnology
Bartolomeo Civalleri, Monique A. van der Veen, Srinidhi Mula, Lorenzo Dona
Summary: This study focuses on the piezoelectric properties of a class of cubic non-centrosymmetric MOFs called zeolitic imidazolate frameworks (ZIFs). Through calculations and analysis of different structures, it was found that CdIF-1 (Cd2+ and -CH3 linker substituent) has the highest piezoelectric coefficient, comparable to that of the quintessential piezoelectric polymer.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Review
Chemistry, Physical
Alessandro Erba, Jacques K. Desmarais, Silvia Casassa, Bartolomeo Civalleri, Lorenzo Dona, Ian J. Bush, Barry Searle, Lorenzo Maschio, Loredana Edith-Daga, Alessandro Cossard, Chiara Ribaldone, Eleonora Ascrizzi, Naiara L. Marana, Jean-Pierre Flament, Bernard Kirtman
Summary: The CRYSTAL program is a quantum-mechanical simulation tool for materials, bridging molecular quantum chemistry and solid state physics. By using atom-centered basis functions and efficient evaluation of the Fock exchange series, it has allowed for a better understanding of various material properties. The program has undergone significant developments in the past five years and has been applied in various fields.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Annika F. Moeslein, Mario Gutierrez, Kirill Titov, Lorenzo Dona, Bartolomeo Civalleri, Mark D. Frogley, Gianfelice Cinque, Svemir Rudic, Jin-Chong Tan
Summary: Metal-organic frameworks (MOFs) have unique functionalities and properties, making them potential materials for chemical sensors and optoelectronics. The ZnQ@OX-1 composite material shows excellent sensing performance due to its visible color change when exposed to acetone. This study presents a multimodal investigation on the vapochromism of the composite material using high-resolution spectroscopy techniques, supported by density functional theory calculations.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Jonas Gosch, Diletta Morelli Venturi, Erik Svensson Grape, Cesare Atzori, Lorenzo Dona, Felix Steinke, Tobias Otto, Tim Tjardts, Bartolomeo Civalleri, Kirill A. Lomachenko, A. Ken Inge, Ferdinando Costantino, Norbert Stock
Summary: The use of V-shaped linker molecules, H2ODB and H2CDB, resulted in the discovery of two isoreticular Ce(IV)-based metal-organic frameworks (MOFs) denoted CAU-58. The synthesis approach in acetonitrile proved effective in accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units. The MOFs exhibited high thermal stabilities and reversible water adsorption, and CAU-58-ODB showed enhanced photocatalytic activity under UV light.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Laura Bonometti, Florian Kraus, Tim Graubner, Antti J. Karttunen, Bartolomeo Civalleri, Lorenzo Dona, Lorenzo Maschio
Summary: In this research, we conducted a comprehensive theoretical and experimental characterization of alpha sodium amide (NaNH2), including novel measured and simulated vibrational spectra (IR and Raman) as well as X-ray diffraction patterns. We proposed a new hypothesis of a low-temperature symmetry breaking of the compound's structure to space group C2/c, contrary to the commonly reported Fddd space group found experimentally. Additionally, we provided a theoretical estimate of the heat of formation of sodium amide from ammonia, which was -12.2 kcal/mol at ambient conditions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Jonas Gosch, Diletta Morelli Venturi, Erik Svensson Grape, Cesare Atzori, Lorenzo Dona, Felix Steinke, Tobias Otto, Tim Tjardts, Bartolomeo Civalleri, Kirill A. Lomachenko, A. Ken Inge, Ferdinando Costantino, Norbert Stock
Summary: The use of V-shaped linker molecules led to the discovery of two Ce(IV)-based MOFs synthesized using a novel acetonitrile solvent approach. The structures of the MOFs were determined using 3D ED, PXRD, and DFT calculations. The MOFs exhibited high thermal stability, and their catalytic activity for the degradation of methyl orange was studied, with CAU-58-ODB showing enhanced photocatalytic activity under UV light.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Alicia Schuitemaker, Julie Aufort, Katarzyna B. Koziara, Raffaella Demichelis, Paolo Raiteri, Julian D. Gale
Summary: The study focuses on the interaction of small organic molecules containing carboxylate and ammonium functional groups with mineral ions in aqueous solution, using rigid-ion and polarizable force fields. The force fields are designed to be compatible with existing models for aqueous calcium carbonate, and their application to ion pairing in aqueous solution is studied in order to quantitatively determine the extent of association.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
