Review
Chemistry, Multidisciplinary
Johanna Heine, Benjamin Peerless, Stefanie Dehnen, Crispin Lichtenberg
Summary: Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable synthetic methods, as well as the development of promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities as they show a spectrum of properties that is yet to be fully exploited. Recent findings highlight the essential contributions to the synthesis, analyses, and utilization of ionic bismuth compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Julia Rienmueller, Andreas Schmidt, Nathan J. Yutronkie, Rodolphe Clerac, C. Gunnar Werncke, Florian Weigend, Stefanie Dehnen
Summary: Lowering the charge of Zintl anions by (element-)organic substituents allows their use as sources of (semi)metal nanostructures. A new strategy was developed using low-coordinate 3d metal complexes as electrophiles, leading to the synthesis of Zintl clusters with uncommon electronic structures and magnetic coupling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Katrin Beuthert, Fuxing Pan, Lukas Guggolz, Robert J. Wilson, Jan Hempelmann, Richard Dronskowski, Stefanie Dehnen
Summary: This article describes the composition of the solid mixture K2GeSb and the salts of novel binary Zintl anions obtained through extraction. Some of the anions discovered are previously unseen, and a new cluster topology was also found.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Fuxing Pan, Rodica Ababei, Werner Massa, Stefanie Dehnen
Summary: The formation and chemistry of P-7(3-) has been extensively studied, while investigations on its heavier congeners Pn(7)(3-) (Pn= As, Sb, Bi), especially Bi-7(3-), have been limited. In this report, new coordination compounds with As-7(3-) and Bi-7(3-) are presented, expanding the rare studies on these compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhejiaji Zhu, Zi-Long Yu, Wen-Yan Gao, Xin Su, Li-Wei Chen, Yu-Chen Hao, Si-Qian Wu, Di Liu, Xiao-Ting Jing, Hui-Zi Huang, An-Xiang Yin
Summary: The electrocatalytic properties of metal nanoparticles can be enhanced by rational design of their compositions and structures. In this study, freestanding intermetallic Au2Bi NPs and Au2Bi/Bi hetero-NPs were synthesized and their electrocatalytic CO2 reduction reaction (CO2RR) performances were investigated. The formation of heterogeneous seeds and the presence of Au components were found to be important for the formation of intermetallic Au2Bi and Au2Bi/Bi hetero-NPs. The alloying of Bi with Au and the formation of heterogeneous interfaces promoted the CO2-to-HCOOH conversion with high activity and selectivity.
Article
Chemistry, Inorganic & Nuclear
Yipeng Zang, Yueyue Wang, Ruili Sang, Li Xu
Summary: The redox reaction of monovalent Rh-2(CO)(4)Cl(2) and Bi-n(n-) (n = 2, 3) in ethylenediamine solution led to the formation of a decabismuthide-hexarhodium dianion [Rh@Bi-10(RhCO)(5)](2-) (1a), where a novel Bi10-bowl was constructed from oxidized 2Bi(3)/2Bi(2) open triangles/dimers. The structure of 1a was stabilized by strong bonding to a reduced Rh@(RhCO)(5) square pyramid. Weak interactions between two 1a dianions formed a dimer [Rh@Bi-10(RhCO)(5)](2)(4-) (1). The structure and bonding of the novel polybismuthide heteroanion 1 are discussed.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Xian-Juan Feng, Matej Bobnar, Swantje Lerch, Harry Biller, Marcus Schmidt, Michael Baitinger, Thomas Strassner, Yuri Grin, Bodo Boehme
Summary: The metastable type-II clathrate Na24-delta Ge136 was obtained through a two-step procedure involving the reaction of Na12Ge17 with benzophenone in an ionic liquid followed by annealing under an argon atmosphere. The resulting product exhibited metallic properties and showed slow aging behavior at room temperature.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Wei-Qiang Zhang, Harry W. T. Morgan, John E. McGrady, Zhong-Ming Sun
Summary: This paper demonstrates the use of binary crown clusters [M@As-8](3-) (M = Nb, Ta) as synthetic precursors, which, when combined with ZnMes(2), generate ternary intermetalloid clusters {M@[As-8(ZnMes)(4)]}(3-) (M = Nb, Ta) with 12-vertex cages. Structural studies, mass spectrometry, and DFT analysis of the electronic structure complement the synthesis. The synthesis of these clusters provides new opportunities for the construction of As-based nanomaterials.
Article
Chemistry, Inorganic & Nuclear
Maria Annette Herz, Kati Finzel, Walter Schnelle, Michael Ruck
Summary: Black needle-shaped crystals of Bi21Rh4Cl6I7 were obtained by slow cooling a melt of Bi, RhI3, and BiCl3. The crystal structure consists of intermetallic rods, anionic groups, and Rh-centered polyhedra bonded to Bi units. The compound shows semiconducting behavior below 240 K and temperature-independent resistance above that.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Physical
Li Yang, Yuan Yuan, Tao Chen, Xu Dai, Ling Zhang, Dajian Li, Aitao Tang, Wang Yi, Lijun Zhang, Fusheng Pan
Summary: The diffusion behavior of Mg-Gd intermetallic compounds was studied in the temperature range of 713-793 K using the diffusion couple method. The mechanical properties of the obtained compounds were analyzed using nanoindentation characterization technique and first principles calculations. The experimental results showed that the hardness of Mg5Gd, Mg3Gd, and Mg2Gd was nearly twice that of the alpha phase (Mg), laying the foundation for the development of high-strength Mg-Gd based Mg alloys.
Article
Nanoscience & Nanotechnology
Sa Ma, Fangzhou Xing, Chunming Deng, Lijun Zhang
Summary: A novel analytical approach was developed for describing the diffusion-controlled simultaneous growth of multilayer stoichiometric compounds in binary reactive diffusion couples. The models were successfully applied to three different real cases, showing a satisfactory agreement with experimental data and potential applications in industries such as joining, coating, and solar cells.
SCRIPTA MATERIALIA
(2021)
Article
Thermodynamics
Xiangyang Liu, Zeyang Kang, Yaohui Shi, Hui Liu, Ying Zhang, Maogang He
Summary: The phase diagrams of binary and ternary mixtures of lead, bismuth, and lead oxide were experimentally determined and analyzed in this study. An optimized model was proposed for accurately predicting the phase diagrams of the mixtures.
FLUID PHASE EQUILIBRIA
(2022)
Article
Materials Science, Coatings & Films
Grzegorz Sadowski, Rui Shu, Arnaud le Febvrier, Zhijia Han, Denis Music, Weishu Liu, Per Eklund
Summary: Mg3Bi2-based compounds have attracted great interest for thermoelectric applications near room temperature. Undoped p-type Mg3SbxBi2-x thin films were successfully synthesized using magnetron sputtering at a growth temperature of 200 ? on different substrates. The synthesized thin films exhibited a La2O3-type crystal structure and showed a semiconductive behavior. Increasing the Bi content was found to improve the electrical resistivity and power factor near room temperature. Thin films synthesized at low temperatures can open up novel possibilities for flexible devices on heat-sensitive substrates.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2023)
Article
Multidisciplinary Sciences
Zhiwei Fu, Qinru Wei, Xiaotong Guo, Xing Fu, Jian Wang, Chao Yang, Huaixin Guo, Jia-Yue Yang
Summary: A numerical analysis is used to establish kinetic models for Cu flux on Cu/Sn/Cu, and these models are verified with reported data. The models discuss the polarity effect of intermetallic compounds (IMCs) growth at different alloying stages. It is found that the net thermodiffusion Cu flux in Cu6Sn5 is over three times larger than that in Cu3Sn before Sn solder is depleted. With current stressing, the thickness of IMCs increases from parabola-like curves to a linear-like relationship.
ADVANCED THEORY AND SIMULATIONS
(2023)
Article
Engineering, Electrical & Electronic
Zeyu Yuan, Yujie He, Ruize Wu, Ming Xu, Jun Zhang, Yunqing Zhu, Qiaoli Wang, Weibin Xie, Huiming Chen
Summary: In this study, the addition of trace amount of rare earth Tb in Sn-3.5Ag-0.5Cu solder was found to delay the formation of IMCs and result in thinner IMC layers. The addition of 0.025 wt% Tb improved shear strength and wettability, while slowing down IMC growth, thus extending the reliability of the joint interface and the service life of the solder joint.
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
(2022)
Article
Chemistry, Multidisciplinary
Armin R. Eulenstein, Yannick J. Franzke, Niels Lichtenberger, Robert J. Wilson, H. Lars Deubner, Florian Kraus, Rodolphe Clerac, Florian Weigend, Stefanie Dehnen
Summary: This study demonstrates the straightforward synthesis of a metal 12-ring with 2 π-aromaticity, showing a stronger ring current than benzene and equivalent to porphine. It indicates the possibility of designing and generating substantial π-aromaticity in large metal rings for potential use in cluster-based reactions.
Article
Chemistry, Physical
Christof Holzer, Yannick J. Franzke, Max Kehry
Summary: This paper presents a comprehensive overview of the performance of local hybrid functionals for various molecular properties and discusses the generalization of kinetic energy and excitation energies. Different ansatze for local mixing functions are compared, with a modified version of the PSTS functional showing consistent improvement. The study highlights the importance of choosing the best local mixing function based on the specific property and molecular class being studied.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Physical
Viktoriia Zubar, Niels Lichtenberger, Mathias Schelwies, Thomas Oeser, A. Stephen K. Hashmi, Thomas Schaub
Summary: The hydrogenation of (+)-Sclareolide to (-)-ambradiol catalyzed by a manganese pincer complex was achieved with high yield. The catalyst is easy to prepare, and the reaction conditions are relatively mild, with reproducible experimental results.
Article
Chemistry, Physical
Yannick J. Franzke, Christof Holzer, Fabian Mack
Summary: The study introduces the extension of the Green's function GW method and the Bethe-Salpeter equation (BSE) to molecular response properties, discussing both one-component and two-component formalisms to accurately study heavy-element systems. The methodology efficiently utilizes conventional central processing units (CPUs) and modern graphics processing units (GPUs) for calculations involving thousands of basis functions, showing the importance of Hartree-Fock exchange in providing a reliable starting point for GW quasi-particle energy calculations. The improved results for NMR coupling constants are achieved through the admixture of Kohn-Sham correlation kernel, leading to remarkable outcomes when combined with other methods like the eigenvalue-only self-consistent variant (evGW) and Becke's half and half functional (BH&HLYP).
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Yannick J. Franzke, Jason M. Yu
Summary: We present a highly efficient implementation of the electron-nucleus hyperfine coupling matrix within the one-electron exact two-component (X2C) theory. Our implementation accurately reproduces the four-component fully relativistic parent results and has been extensively benchmarked on transition-metal compounds and rare-earth single-molecule magnets.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Yannick J. Franzke, Jason M. Yu
Summary: We present an exact two-component (X2C) ansatz for the EPRg tensor using gauge-including atomic orbitals (GIAOs) and a magnetically balanced basis set expansion. This implementation results in a gauge-origin-invariant formalism and accurately reproduces the results of the parent four-component relativistic theory. The use of the diagonal local approximation to the unitary decoupling transformation helps reduce computational costs.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Yannick J. Franzke, Christof Holzer
Summary: Meta-generalized gradient approximations (meta-GGAs) and local hybrid functionals often rely on the kinetic energy density tau. This study extends previous approaches based on the current density to investigate the impact on paramagnetic nuclear magnetic resonance (NMR) shieldings and electron paramagnetic resonance (EPR) g-tensors. The results show significant improvements, especially for the Minnesota and SCAN functional families, suggesting the use of the current density generalized tau in paramagnetic NMR and EPR calculations.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Christof Holzer, Yannick J. Franzke
Summary: This study designed a local hybrid functional without relying on benchmark data but constructed it in a more ab initio manner following the principles of modern meta-generalized gradient approximations and considering theoretical constraints. The new exchange functional showed robust performance in various properties, but lost some ground in NMR shifts.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Florian Bruder, Yannick J. Franzke, Florian Weigend
Summary: Temperature-dependent Fermi-contact and pseudocontact terms play important roles in the paramagnetic NMR shielding tensor. In this study, we assess the accuracy of a perturbative ansatz by combining the scalar relativistic (local) exact two-component (X2C) framework with spin-orbit perturbation theory, including the screened nuclear spin-orbit correction. The results show that the Fermi-contact and pseudocontact interaction is well-described for paramagnetic NMR shifts, but larger deviations are found for the EPR spectra and the principle components of the EPR properties of heavy elements.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Frederic Kraetschmer, Sun Xiaofei, Sebastian Gillhuber, Hannes Kucher, Yannick J. Franzke, Florian Weigend, Peter W. Roesky
Summary: This article describes the synthesis of a novel bis-stannylene pincer ligand and its complexation with coinage metals (Cu-I, Ag-I and Au-I). In the solid state, all coinage metal centers are in tetrahedral coordination environments and are exclusively coordinated by four neutral Sn-II donors. Sn-119 NMR provided information about the behavior in solution. All of the isolated compounds have photoluminescent properties, and these were investigated at low and elevated temperatures. Compared to the free bis-stannylene ligand, coordination to coinage metals led to an increase in the luminescence intensity. The new compounds were investigated in detail through all-electron relativistic density functional theory (DFT) calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Christof Holzer, Yannick J. Franzke, Ansgar Pausch
Summary: In this paper, a consistent current DFT approach for relativistic DFT, including spin-orbit coupling, is introduced. The importance of current density terms for various properties is assessed, and it is found that CDFT plays a crucial role in describing spin-orbit interactions, particularly with significant impact on EPR properties.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Yannick J. Franzke
Summary: This article presents a self-consistent and complex spin-orbit exact two component (X2C) formalism for NMR spin-spin coupling constants. It reduces the method to a scalar one component approximation while partitioning the first-order response term into Fermi-contact (FC) and spin-dipole (SD) interactions, as well as the paramagnetic spin-orbit (PSO) contribution. The relativistic one-component approach is combined with a modern density functional treatment, reducing computational demands significantly. However, limitations are identified for tin compounds containing heavy halogen atoms, where the one-component treatment is inadequate.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Yannick Franzke, Christof H. Holzer, Josefine H. Andersen, Tomislav Begusic, Florian Bruder, Sonia Coriani, Fabio Della Sala, Eduardo Fabiano, Daniil A. Fedotov, Susanne Fuerst, Sebastian Gillhuber, Robin Grotjahn, Martin Kaupp, Max Kehry, Marjan Krstic, Fabian Mack, Sourav Majumdar, Brian D. Nguyen, Shane M. Parker, Fabian Pauly, Ansgar Pausch, Eva Perlt, Gabriel S. Phun, Ahmadreza Rajabi, Dmitrij Rappoport, Bibek Samal, Tim Schrader, Manas Sharma, Enrico Tapavicza, Robert S. Tress, Vamsee Voora, Artur Wodynski, Jason M. Yu, Benedikt Zerulla, Filipp Furche, Christof Haettig, Marek Sierka, David P. Tew, Florian Weigend
Summary: TURBOMOLE is an optimized software suite for large-scale quantum-chemical and materials science simulations. It offers robust and fast applications in various fields, including catalysis, chemistry, spectroscopy, and biochemistry. This Perspective provides an overview of TURBOMOLE's functionality, recent developments, and upcoming features, showcasing its continuous growth and expansion in electronic structure methods, molecular properties, and modeling capabilities.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Yannick J. Franzke
Summary: This article introduces a simplified self-consistent and complex spin-orbit (NMR) interaction constant for two-component (X2C) formalism. First, the first-order response terms are divided into the Fermi-contact (FC) and spin-dipole (SD) interactions, as well as the paramagnetic spin-orbit (PSO) contributions. The FC+SD terms are real and symmetric, while the PSO term is purely imaginary and antisymmetric. Then, the relativistic one-component method is combined with a modern density functional method, including the response of the current density. The computational demands are reduced by factors of 8-24, as demonstrated for a large tin compound consisting of 137 atoms. The limitations of the current approach are critically evaluated for Sn, Pb, Pd, and Pt compounds, indicating that the one-component treatment is insufficient for tin compounds with heavy halogen atoms.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Florian Bruder, Yannick J. Franzke, Christof Holzer, Florian Weigend
Summary: An efficient implementation method for zero-field splitting parameters is proposed in this paper, and its accuracy and efficiency are evaluated. This method has broad application prospects and significant research significance in fields such as transition metals and main-group compounds.
JOURNAL OF CHEMICAL PHYSICS
(2023)
