Article
Materials Science, Multidisciplinary
Luke J. Wirth, Christopher Woodward, Amir A. Farajian
Summary: Advances in first principles methods are used to study the atom-vacancy exchanges near a screw dislocation in fcc Ni, revealing direction-dependent free energy profiles and temperature-dependent correlation effects. The dynamic approach shows intra-cell energy profile asymmetry related to dynamic geometry rearrangements. Despite absolute values of rate constants being similar, the HTST method generally underestimates rates by a factor of 2-5, partially explaining discrepancies between theoretical works and experiments in pipe diffusion diffusivities.
Article
Chemistry, Multidisciplinary
J. Patrick Zobel, Anna M. Wernbacher, Leticia Gonzalez
Summary: The mechanism of reverse intersystem crossing (rISC) in metal-based TADF emitters is still not clear, as the small singlet/triplet energy gaps necessary for thermal rISC in donor-acceptor systems with charge-transfer excited states have spin-orbit couplings that are too small for effective rISC. In this study, the first nonadiabatic dynamics simulation of rISC process in a carbene-copper(I)-carbazolyl TADF emitter is reported. Efficient rISC on a picosecond time scale is demonstrated, involving an intermediate higher-lying triplet state of metal-to-ligand charge transfer character ((MLCT)-M-3) that enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S-1 state where the complex can return to a co-planar coordination geometry with high fluorescence efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xavier Lopez, Tjerk P. Straatsma, Aitor Sanchez-Mansilla, Coen de Graaf
Summary: This computational study investigates singlet fission as a means for multiplying photogenerated excitons in crystalline polyacenes. The results show that pentacene has smaller singlet fission coupling compared to B,N-pentacene. The introduction of molecular disorder affects the singlet fission efficiency, with some structures exhibiting larger coupling when charge transfer and excited singlet and triplet states are nearly degenerate.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Multidisciplinary Sciences
Zhiyu He, Melanie Roedel, Julian Luetgert, Armin Bergermann, Mandy Bethkenhagen, Deniza Chekrygina, Thomas E. Cowan, Adrien Descamps, Martin French, Eric Galtier, Arianna E. Gleason, Griffin D. Glenn, Siegfried H. Glenzer, Yuichi Inubushi, Nicholas J. Hartley, Jean-Alexis Hernandez, Benjamin Heuser, Oliver S. Humphries, Nobuki Kamimura, Kento Katagiri, Dimitri Khaghani, Hae Ja Lee, Emma E. McBride, Kohei Miyanishi, Bob Nagler, Benjamin Ofori-Okai, Norimasa Ozaki, Silvia Pandolfi, Chongbing Qu, Divyanshu Ranjan, Ronald Redmer, Christopher Schoenwaelder, Anja K. Schuster, Michael G. Stevenson, Keiichi Sueda, Tadashi Togashi, Tommaso Vinci, Katja Voigt, Jan Vorberger, Makina Yabashi, Toshinori Yabuuchi, Lisa M. Zinta, Alessandra Ravasio, Dominik Kraus
Summary: The extreme conditions inside ice giants like Uranus and Neptune have been found to lead to peculiar chemical reactions and structural transitions, resulting in the formation of diamonds or superionic water. This study provides important insights into the chemistry and structure of ice giants and offers a new method for producing nanodiamonds by shock-compressing plastic.
Article
Chemistry, Physical
Yasmine S. Al-Hamdani, Andrea Zen, Dario Alfe
Summary: Molecular hydrogen has the potential to reduce carbon dioxide emissions, but hydrogen gas storage is a major bottleneck. Physisorbing molecular hydrogen at ambient pressure and temperatures is a promising alternative. However, understanding hydrogen adsorption in well-defined nanomaterials remains experimentally challenging.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Peng Song, Zhufeng Hou, Pedro Baptista de Castro, Kousuke Nakano, Kenta Hongo, Yoshihiko Takano, Ryo Maezono
Summary: Based on recent studies on high-temperature LaY ternary hydrides, a genetic algorithm and ab initio calculations were used to investigate the phase and structural stabilities. New crystal structures were discovered, with Cmmm phases showing a Tc of approximately 140 K at around 200 GPa due to high electron phonon coupling constant. The study evaluated superconductivity properties of different phases and their stability against decomposition.
CHEMISTRY OF MATERIALS
(2021)
Article
Green & Sustainable Science & Technology
Yifei Yuan, Ryan Sharpe, Kun He, Chenghang Li, Mahmoud Tamadoni Saray, Tongchao Liu, Wentao Yao, Meng Cheng, Huile Jin, Shun Wang, Khalil Amine, Reza Shahbazian-Yassar, M. Saiful Islam, Jun Lu
Summary: Rechargeable aqueous Zn-MnO2 technology combines favorable sustainability characteristics, including safety, cost, and environmental compatibility. Advanced characterizations and theoretical calculations provide fresh insight into the charge storage mechanism, closing an ongoing debate and suggesting ways forward.
NATURE SUSTAINABILITY
(2022)
Article
Chemistry, Physical
Leszek M. Malec, Mateusz Z. Brela, Katarzyna M. Stadnicka
Summary: This work investigates the dynamic character of hydrogen-bond networks in two three-component crystals comprising polycationic chains. X-ray diffraction measurements and molecular dynamics computations were used to study the hydrogen-bond systems in both crystals, revealing proton transfer phenomena occurring at 300 K.
Article
Multidisciplinary Sciences
Anupam Bhattacharya, Vishal Bhardwaj, Brajesh K. Mani, Jayanta K. Dutt, Ratnamala Chatterjee
Summary: This study investigates rare-earth half-Heusler alloys under strain using first-principles simulations and reveals multiple band inversions associated with topological phase transitions, leading to changes in surface electronic transport in triple point semi-metallic phases. Further application of strain does not increase the number of triple points and Fermi arcs, but affects the momentum of triple point crossings.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Physical
Zachary K. Goldsmith, Annabella Selloni, Zhutian Ding
Summary: In this study, hole states at the aqueous interface of Zn-doped hematite (0001) were characterized using density functional theory. A hole state within the band gap of hematite, localized on a Fe-O moiety, was observed. The interfacial hydration structure and hydrogen bonding dynamics were minimally affected by Zn doping.
Article
Chemistry, Multidisciplinary
Solana Di Pino, Yamila A. Peerez A. Sirkin, Uriel N. Morzan, Veronica M. Sanchez, Ali Hassanali, Damian A. Scherlis
Summary: Nanoconfinement effects on water dissociation and reactivity at interfaces, pores, or aerosols remain controversial. Using ab initio simulations, we demonstrate that water dissociation is conserved intact to unexpectedly small length-scales, down to aggregates of only a dozen molecules or pores of widths below 2 nm. This work provides a fundamental description of water dissociation at different scales with implications on reactivity at the air-liquid interface.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Francisco M. Fernandez, Javier Garcia
Summary: The potential energy curves of the hydrogen molecular ion were computed using the Riccati-Pade method in the Born-Oppenheimer approximation. The results obtained are the most accurate so far, and additional benchmark values are made available through the provided software.
Article
Chemistry, Applied
Yufan Xia, Zijian Hong, Linming Zhou, Shuang Chen, Zhen Luo, Shoutong Jin, Yuhui Huang, Yinzhu Jiang, Yongjun Wu
Summary: In this study, a multiscale simulation platform was built to comprehensively investigate the adsorption process of amino acids on the Zn metal surface. The study found that adsorption sites, adsorbate-surface angle, and average distance are critical parameters for the stability and strength of surface adsorption. It was also discovered that amino acids prefer to align parallel to the Zn metal surface, leading to better surface protection against corrosion and preventing dendrite growth.
JOURNAL OF ENERGY CHEMISTRY
(2023)
Article
Chemistry, Physical
Philippe F. Weck, Nathan W. Moore
Summary: The equations of state for different polymorphs of Nb2O5 were investigated, and shock Hugoniot curves were predicted using ab initio molecular dynamics simulations. The simulated results were consistent with experimental measurements of phase transitions and pressure-induced amorphization.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Jinchang Fan, Yunlong Zhang, Wei Liu, Mingrun Li, Yafeng Cai, Qinqin Ji, Zhenchao Zhao, Guangjin Hou, Aowen Li, Wu Zhou, Liang Yu, Dehui Deng
Summary: This study reports the construction of ambient-stable two-dimensional rhodium hydride nanosheets for the first time, achieved through a ligand confinement effect. The 2D RhH exhibits superior hydrogen evolution reaction (HER) activity compared to 2D Rh catalyst and commercial Pt/C catalyst. Theoretical calculations reveal the significant role of interstitial H atoms and surface ligands in enhancing the HER activity of Rh.
Article
Chemistry, Organic
Hong-Gang Cheng, Maoping Pu, Gourab Kundu, Franziska Schoenebeck
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Minh Hieu Nguyen, Maoping Pu, Luoqiang Zhang, Yonggui Robin Chi, Yun-Dong Wu, Jianrong Steve Zhou
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Siqi Liu, Maoping Pu, Yun-Dong Wu, Xinhao Zhang
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Shenghan Teng, Yonggui Robin Chi, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Jianrong Steve Zhou
Summary: The nickel-catalyzed intermolecular Heck reaction of cycloalkenes with aryl triflates, mesylates, and tosylates shows excellent enantiomeric ratios. Additionally, the asymmetric reductive Heck reaction is also applicable to a 2-cyclopentenone ketal, equivalent to conjugate arylation of the enone itself.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Fei Tan, Maoping Pu, Jun He, Jinzhao Li, Jian Yang, Shunxi Dong, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study describes an enantioselective homologation of ketones with alpha-alkyl alpha-diazo esters using a chiral scandium(III) N,N'-dioxide catalyst to produce a series of optically active beta-keto esters with an all-carbon quaternary center. This method provides a highly selective and synthetically efficient strategy for the synthesis of enantioenriched compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wei Yang, Maoping Pu, Xiaobin Lin, Min Chen, Yanji Song, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: In this study, a novel method was developed for the synthesis of vinyl gamma-amino amides with high gamma-selectivity and enantioselectivity using a high-spin chiral complex catalyst. The calculation showed a spin state change from quartet cobalt(II) complex to doublet Co(II)-carbene species for Z-selective and enantioselective nucleophilic addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wen Liu, Maoping Pu, Jun He, Tinghui Zhang, Shunxi Dong, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study presents an efficient enantioselective radical carboazidation and diazidation reaction of α,β-unsaturated ketones and amides catalyzed by chiral N,N'-dioxide/Fe(OTf)(2) complexes, enabling the preparation of chiral compounds from substituted alkenes. Control experiments and mechanistic studies confirmed the radical pathway in the reaction process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Daoyong Zhu, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: This study revealed that palladium catalyzes a domino Heck arylation and alkylation of nonconjugated cyclodienes to produce trans isomers of disubstituted cyclohexenes with exceptionally high enantiomeric ratios. Through DFT calculations and experiments, it was demonstrated that the interaction between the two CF bonds of Josiphos and the sodium ion of malonates facilitates stereoselective allylic attack. This represents a new type of attractive noncovalent interactions discovered in organometallic catalysis.
Article
Chemistry, Multidisciplinary
Long Chen, Maoping Pu, Shiyang Li, Xinpeng Sang, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: The construction of quaternary carbon centers with chiral selectivity is a significant challenge in asymmetric catalysis research. Using a chiral N,N'-dioxide-Co(II) complex, an efficient enantioselective Michael reaction was achieved for the synthesis of nitrile-, aryl-, and dialkyl-bearing carbon centers, with applications in the divergent synthesis of pharmaceuticals and natural products. The through-space dispersion interactions between unbound silyl ketene imines and the 1-acrylpyrazole-bonded catalyst are crucial for facilitating the reactivity and enantioselectivity of the process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaobin Lin, Maoping Pu, Xinpeng Sang, Shiyang Li, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study reports the enantioselective cycloaddition reaction between thioketones and alpha-diazo pyrazoleamides, leading to the direct synthesis of tetrasubstituted thiiranes, which can be further transformed into tetrasubstituted olefins through desulfuration. The reaction is catalyzed by chiral N,N'-dioxide/cobalt(II) complexes and exhibits high efficiency and stereoselectivity. This work provides a route for selectively constructing challenging compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Luoqiang Zhang, Xiuhua Wang, Maoping Pu, Caiyou Chen, Peng Yang, Yun-Dong Wu, Yonggui Robin Chi
Summary: Nickel catalysts with chiral pyrox ligands were used for enantioselective reductive arylation and heteroarylation of aldimines using (hetero)aryl halides and sulfonates. Crude aldimines generated from the condensation of aldehydes and azaaryl amines can also be used for catalytic arylation. The mechanism involves an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines, as supported by density functional theory (DFT) calculations and experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qianwen He, Mao-Ping Pu, Zheng Jiang, Hongyu Wang, Xiaoming Feng, Xiaohua Liu
Summary: A chiral cobalt complex was reported as a catalyst for the enantioselective epoxidation of cyclic and acyclic trisubstituted alkenes. The chiral complex played a crucial role in the formation of Co-O intermediate and enantioselective electrophilic oxygen transfer. Mechanistic studies and DFT calculations confirmed the formation of Co-O species as a quartet Co(III)-oxyl tautomer. The origin of enantioselectivity was elucidated through control experiments, nonlinear effects, kinetic studies, and DFT calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Guihua Pan, Maoping Pu, Hongyu Wang, Meijia Ying, Yi Li, Shunxi Dong, Xiaoming Feng, Xiaohua Liu
Summary: A solid-liquid phase-transfer strategy was devised to control the generation speed of arynes, enabling a catalytic enantioselective nucleophilic addition reaction with good stereoselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Tinghui Zhang, Ziwei Zhong, Zi Zeng, Zitong Zhu, Fei Wang, Yuxin Zhang, Xiaohua Liu, Maoping Pu, Xiaoming Feng
Summary: The asymmetric synthesis of enantioenriched C3-arylated oxindoles has been achieved via the Friedel-Crafts alkylation of 3-bromo-3-substituted oxindoles with arenes and heteroarenes, using a chiral N,N'-dioxide/transition metal complex as the catalyst.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Thomas Scattolin, Maoping Pu, Franziska Schoenebeck
CHEMISTRY-A EUROPEAN JOURNAL
(2018)