News Item
Chemistry, Multidisciplinary
Yoshito Tobe
Summary: An overcrowded alkene with open-shell tetraradical character has been synthesized, in which the interaction between the pi-conjugated subunits depends on the charge and spin state.
Article
Chemistry, Multidisciplinary
Bibek Prajapati, Duy-Khoi Dang, Piotr J. Chmielewski, Marcin A. Majewski, Tadeusz Lis, Carlos J. Gomez-Garcia, Paul M. Zimmerman, Marcin Stcpieit
Summary: The study presents a hexaradicaloid molecule with alternating Kekule and non-Kekule connectivities, showing a singlet ground state with significant hexaradicaloid character. It exhibits multiple thermally accessible high-spin states and undergoes two consecutive one-electron oxidations at low potentials. This design strategy provides a new approach for multistate spin switches and redox-amphoteric NIR dyes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mahendra K. Sharma, Dennis Rottschafer, Timo Glodde, Beate Neumann, Hans-Georg Stammler, Rajendra S. Ghadwal
Summary: The text discusses the isolation of the first Sn-I diradical based on an anionic dicarbene scaffold, its molecular structure, and chemical reactivity with different compounds like PhSeSePh and MeOTf. The diradical exhibits a diatropic ring current and a small singlet-triplet energy gap, indicating its potential for further study in terms of its electronic properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Wangdong Zeng, Jishan Wu
Summary: The electronic properties of finite-sized graphene fragments are strongly dependent on their topological structures, especially when they possess extended zigzag edges. Synthesis of open-shell molecules with unique magnetic activity is challenging, and can be predicted and analyzed using Clar's sextets and density functional theory. Their magnetic activity and quantum properties make them promising materials for carbon-based spintronic and quantum devices.
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Markus Balmer, Carsten von Haenisch, C. Gunnar Werncke
Summary: The synthesis and characterization of the first homoleptic open-shell transition metal phosphinidenide is presented. Interestingly, the highly reducing phosphinidenide [(sIDipp)P](-) cannot be stabilized in an analogous fashion by coordination to a low-coordinate high-spin iron(ii) center. Through reactions involving [MnL2] and [(sIDipp)PK], the formation process and unexpected observations were documented.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Cong Wang, Inga S. Ulusoy, Lucas E. Aebersold, Angela K. Wilson
Summary: This article discusses the multi-configuration electron-nuclear dynamics for open shell systems using a spin-unrestricted formalism. Mean fields are evaluated using second-order reduced density matrices for electronic and nuclear degrees of freedom. Applications to light-element diatomics, including equilibrium geometries, electronic energies, dipole moments, and absorption spectra, are presented, along with comparisons of von Neumann entropies for different spin states of a LiH molecule.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Katharina Boguslawski
Summary: The pair coupled cluster doubles (pCCD) ansatz is an inexpensive and accurate method for describing multi-reference problems in closed-shell systems. This method has been extended to handle open-shell molecules with up to 4 unpaired electrons, approaching chemical accuracy while remaining computationally efficient. The performance of these methods is comparable to more expensive models like DMRG or CCSD(T).
CHEMICAL COMMUNICATIONS
(2021)
Article
Engineering, Multidisciplinary
H. Mellouli, H. Mallek, M. Wali, F. Dammak, F. Gamaoun, A. Abdulrahman
Summary: This paper discusses the static linear analysis of three-dimensional shell structures reinforced by Functionally Graded Carbon Nanotubes Reinforced Composite (FG-CNTRC) using continuum based shell elements. The paper presents a finite element formulation that incorporates the extensible double directors theory and an upgrade parameter for thickness stretching. Four new elements are developed, which enhance the thickness strain and membrane strains through the Enhanced Assumed Strain (EAS) method. The developed methodology is evaluated by examining the deflections and stresses of various shell structures under different parameters.
ENGINEERING ANALYSIS WITH BOUNDARY ELEMENTS
(2022)
Article
Chemistry, Physical
Tingting Zhao, Megan Simons, Devin A. Matthews
Summary: In this study, we extend the least-squares tensor hypercontraction (LS-THC) method to open-shell systems by employing diagrammatic techniques and explicit spin summation. The resulting LS-THC-MP2 and LS-THC-MP3 methods exhibit high accuracy and robustness in studying the reactivity of open-shell species, while significantly reducing computational complexity and costs.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Analytical
Petra Itterheimova, Petr Kuban
Summary: A fully automated, open source capillary electrophoresis (CE) autosampler has been developed, capable of handling up to 14 different samples as a modular component of any in-house built CE instrument. It is operated by an Arduino Mega microcontroller and allows fully programmable injection sequence.
ANALYTICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Hong Ma, Yubing Si, Lan-Lan Luo, Zhao-Yang Wang, Shuang-Quan Zang, Thomas C. W. Mak
Summary: In this study, a bimetallic nanocluster composed of silver and copper was successfully synthesized by introducing a copper precursor. The role of the copper precursor in determining the final structure was observed. Additionally, the optical absorption properties of different nanoclusters were compared and studied in detail.
Article
Chemistry, Multidisciplinary
Theresa E. Rieser, Renita Thim-Spoering, Dorothea Schaedle, Peter Sirsch, Rannveig Litlabo, Karl W. Toernroos, Caecilia Maichle-Moessmer, Reiner Anwander
Summary: Group 3- and 4f-element organometallic chemistry and reactivity are influenced by the size and properties of rare-earth-metal/lanthanide ions. A new reaction protocol allowed the synthesis of terminal imides of open-shell lanthanide cations Ce(III), Nd(III), and Sm(III). Factors such as ion size, metal alkyl properties, steric factors, solvent presence, and aromatic amine properties affect the formation of terminal imides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xiushang Xu, Satoshi Takebayashi, Hiroki Hanayama, Serhii Vasylevskyi, Takatsugu Onishi, Hirokazu Tada, Tatsuhiko Ohto, Akimitsu Narita
Summary: We present the in situ generation and characterization of a BIA derivative as a high diradical open-shell biaryl. The ground state of BIA diradical was determined to be a singlet state with a nearly degenerate triplet state through theoretical calculations and variable-temperature EPR analyses. These findings offer new insights into the design of open-shell biaryls.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiushang Xu, Satoshi Takebayashi, Hiroki Hanayama, Serhii Vasylevskyi, Takatsugu Onishi, Tatsuhiko Ohto, Hirokazu Tada, Akimitsu Narita
Summary: We present the synthesis of a 6,6'-biindeno[1,2-b]anthracene (BIA) derivative as a high diradical open-shell biaryl, characterized by various spectroscopic techniques. Theoretical calculations and EPR analyses reveal its singlet ground state with a nearly degenerate triplet state, shedding light on the design of unique open-shell biaryls.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Analytical
Zhuo Li, Alim Abdurahman, Yimeng Zhang, Hongbin Mu, Yuezhu Feng, Shuwen Guan, Ming Zhang, Feng Li
Summary: In this study, a sensor based on the disappearance of optical and magnetic signals of luminescent radicals caused by the conversion from open-shell into closed-shell molecules was developed. A multiple-channel Cysteine (Cys) probe was created using a luminescent tris(2,4,6-trichloro-3-nitrophenyl) methyl radical (TTM·-3NO2), exhibiting good selectivity and high sensitivity. The reaction between Cys and TTM·-3NO2 was confirmed to generate closed-shell molecules, resulting in changes in fluorescence, colorimetry, and electron paramagnetic resonance (EPR) of the radical. This study not only presents a promising Cys probe, but also demonstrates a novel application of organic radicals in sensing.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Review
Chemistry, Physical
Teng-Teng Chen, Ling Fung Cheung, Lai-Sheng Wang
Summary: Photoelectron spectroscopy combined with quantum chemistry is a powerful method to study the structures and bonding of size-selected boron clusters. Metal-doped boron clusters not only exhibit novel structures, but also provide insights into the metal-boron bonds critical for understanding boride materials. Recent advances in transition metal-doped boron clusters include the discovery of metal-boron multiple bonds and novel aromatic boron clusters.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Wei-Jia Chen, Yang-Yang Zhang, Wan-Lu Li, Hyun Wook Choi, Jun Li, Lai-Sheng Wang
Summary: Photoelectron spectroscopy and quantum chemistry studies were used to investigate the structure and bonding of AuB8-. The research revealed that AuB8- possesses a unique chair-like structure, with Au+ bonded to the edge of the doubly-aromatic B-8(2-) borozene, forming a unique Au-borozene bond.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
G. Stephen Kocheril, Han-Wen Gao, Dao-Fu Yuan, Lai-Sheng Wang
Summary: The development of ion traps as cooling devices has transformed ion spectroscopy, enabling efficient vibrational and rotational cooling for high-resolution experiments. A new experimental apparatus combining a cryogenic 3D Paul trap with a laser vaporization cluster source has been utilized for high-resolution photoelectron imaging of cold cluster anions, demonstrating efficient cooling of BiO- and BiO2- and accurate measurement of their electron affinities and vibrational frequencies.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Editorial Material
Chemistry, Physical
Michele Ceriotti, Lasse Jensen, David E. Manolopoulos, Todd Martinez, David R. Reichman, Francesco Sciortino, C. David Sherrill, Qiang Shi, Carlos Vega, Lai-Sheng Wang, Emily A. Weiss, Xiaoyang Zhu, Jenny Stein, Tianquan Lian
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
G. Stephen Kocheril, Han-Wen Gao, Lai-Sheng Wang
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Anton S. Pozdeev, Wei-Jia Chen, Hyun Wook Choi, Maksim Kulichenko, Dao-Fu Yuan, Alexander I. Boldyrev, Lai-Sheng Wang
Summary: Copper is capable of mediating the formation of bilayer borophenes. Copper-boron binary clusters are used to investigate the interactions between copper and boron, which are crucial for understanding the growth mechanisms of borophenes on copper substrates. In this study, joint photoelectron spectroscopy and theoretical calculations were conducted on two di-copper-doped boron clusters, Cu2B3 (-) and Cu2B4 (-). Well-resolved photoelectron spectra were obtained, revealing the presence of low-lying isomers in both cases. Theoretical calculations showed that the global minimum structures of Cu2B3 (-) and Cu2B4 (-) have different arrangements of copper and boron atoms.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Dao-Fu Yuan, Yuan Liu, Yue-Rou Zhang, Lai-Sheng Wang
Summary: The first observation of a polarization-assisted dipole-bound state (DBS) for a molecule with a dipole moment below 2.5 debye is reported. Photoelectron and photodetachment spectroscopies are conducted and a DBS is found only 6 cm-1 below the detachment threshold along with sharp vibrational Feshbach resonances. The observed DBS has pi-symmetry stabilized by the strong anisotropic polarizability of indolyl.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
G. Stephen Kocheril, Han-Wen Gao, Lai-Sheng Wang
Summary: We conducted a temperature-controlled photoelectron imaging study on SbO2-, which was produced from a laser vaporisation source and cooled in a cryogenic 3D Paul trap. We obtained vibrationally resolved photoelectron spectra for the ground state detachment transition and determined the bending frequencies for both SbO2 and SbO2-. Franck-Condon simulations allowed us to estimate the vibrational temperature of the trapped SbO2- anion. We also obtained a near-threshold spectrum of SbO2- at a photon energy of 3.4958 eV, revealing partially resolved rotational structure and providing an accurate measurement of the electron affinity of SbO2.
Article
Chemistry, Physical
Han-Wen Gao, Hyun Wook Choi, Jie Hui, Wei-Jia Chen, G. Stephen Kocheril, Lai-Sheng Wang
Summary: We report a study on the electronic structure and chemical bonding of the BiB molecule using high-resolution photoelectron imaging. By eliminating vibrational hot bands, we resolved the complicated detachment transitions due to the open-shell nature of BiB and the strong spin-orbit coupling. This study provides a wealth of information about the low-lying electronic states and spin-orbit coupling of BiB.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Yue-Rou Zhang, Dao-Fu Yuan, Lai-Sheng Wang
Summary: Molecular anions with polar neutral cores can support highly diffused dipole-bound states below their detachment thresholds. Recent experimental advances have allowed the investigation of dipole-bound excited states at a new level. This Perspective describes recent progress in the investigation of dipole-bound states using an electrospray photoelectron spectroscopy apparatus equipped with a cryogenically cooled Paul trap.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Yue-Rou Zhang, Dao-Fu Yuan, Chen-Hui Qian, Guo-Zhu Zhu, Lai-Sheng Wang
Summary: Although the influence of molecular polarizability on the formation of dipole-bound states (DBSs) is not well understood, this study investigates the role of polarization interactions in the formation of DBSs using carbazolide as a model compound. The study utilizes cryogenic photodetachment spectroscopy and high-resolution photoelectron spectroscopy and reveals the presence of a polarization-assisted DBS, despite the carbazolyl neutral core having a dipole moment smaller than the critical value. The study also provides valuable information about the vibrational modes and electronic states of carbazolide.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anton S. Pozdeev, Wei-Jia Chen, Maksim Kulichenko, Hyun Wook Choi, Alexander I. Boldyrev, Lai-Sheng Wang
Summary: Researchers have discovered that copper-boron binary clusters have unique covalent bonding structures, which are determined by the high stability of the appropriate-sized boron chain structures in this range. In larger boron chain structures, it is expected that ionic bonding between copper and boron will occur.
SOLID STATE SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Zhen-Ling Wang, Teng-Teng Chen, Wei-Jia Chen, Wan-Lu Li, Jing Zhao, Xue-Lian Jiang, Jun Li, Lai-Sheng Wang, Han-Shi Hu
Summary: In this study, a doubly aromatic triatomic lanthanide-boron molecule, PrB2-, was discovered based on joint photoelectron spectroscopy and quantum chemical investigation. The compound exhibits a C-2v triangular structure and a paramagnetic triplet B-3(2) electronic ground state. Chemical bonding analyses reveal the sigma and pi double aromaticity and multiple Pr-B bonding characters of this compound, showcasing the smallest 4f-metalla-aromatic system.
