Article
Biochemistry & Molecular Biology
Attila Bende, Alex-Adrian Farcas
Summary: The stacking distance between benzene monomers decreases in the first electronic excited state due to stronger intermolecular interaction energy. Intermolecular-type conical intersection (CI) geometries can be formed between the two benzene molecules when both monomer rings undergo planar deformation and weaker C-C bonds are formed between them. These intermolecular-type CIs are energetically more favorable than dimeric CIs with only one deformed monomer. Other CI geometries characterized by the relative rotation of monomers also exist.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Jie Peng, Xin He, Yao Li, Jianxin Guan, Baihua Wu, Xinmao Li, Zhihao Yu, Jian Liu, Junrong Zheng
Summary: Understanding the mechanisms of aggregation-induced emission (AIE) is crucial for the design of better AIE-gens. Diphenylethylene (DPE) featured molecules, with their propeller structure, are important AIE-gens. Through ultrafast UV/IR spectroscopy and theoretical calculations, three representative DPE-featured AIE-gens, triphenylethylene, cis-stilbene, and trans-stilbene, were investigated. The results suggest that crossing conical intersections (CIs) with flexible structural evolutions in solutions reduces fluorescence, while crossing CIs is restricted in solids, leading to no fast nonradiative decay competing with spontaneous emission.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Daniel Keefer, Jeremy R. Rouxel, Flavia Aleotti, Francesco Segatta, Marco Garavelli, Shaul Mukamel
Summary: Research demonstrates that using a resonant infrared field at conical intersections can enhance coherence features of photoisomerization reactions and bring signals of conical intersections above the detection threshold.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Jacob Whitlow, Zhubing Jia, Ye Wang, Chao Fang, Jungsang Kim, Kenneth R. Brown
Summary: This article presents a quantum simulation of conical intersections using a trapped atomic ion system, and experimentally observes the manifestation of geometric phase, demonstrating the advantage of combining spin and motion for quantum simulation of chemical reactions.
Article
Optics
Guanhua Ren, Lu Zhou, Ligang Chen, Liyuan Liu, Jianbing Zhang, Hongwei Zhao, Jiaguang Han
Summary: Terahertz spectroscopy serves as a powerful tool for monitoring crystallization and isomerization processes of molecules, with results showing the formation of a new phase is dependent on cooling rate and investigation of thermal- and photo-induced isomerization processes based on distinctive spectral features of isomers.
Article
Chemistry, Multidisciplinary
Yoonsu Park, Scott P. Semproni, Hongyu Zhong, Paul J. Chirik
Summary: A new four-coordinate cobalt-imido complex was synthesized, exhibiting unique magnetic and thermal properties. This research provides insights into the stability and selectivity of the product through transition state analysis and DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Spiridoula Matsika
Summary: This review focuses on the electronic structure aspects of nonadiabatic processes, discussing the requirements for describing conical intersections and nonadiabatic couplings, the performance of common excited state methods in describing these effects, and recent developments in expanding methodology and implementing nonadiabatic couplings.
Article
Chemistry, Physical
Deependra Jadoun, Markus Kowalewski
Summary: Conical Intersections (CIs) are common in molecular and biological systems, opening up ultrafast nonradiative decay channels. While photoelectron spectroscopy with femtosecond pulses can resolve the involved electronic states in the energy domain, observing the created electronic coherence in the time domain requires probe pulses with larger bandwidth.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Jeremy O. Richardson
Summary: In recent years, machine learning has been successful in simulating molecules in their ground electronic state through fitting ab initio potential-energy surfaces. However, to extend this to excited-state dynamics, nonadiabatic coupling vectors (NACs) must also be learned. Learning NACs in systems with conical intersections is challenging due to their double-valued nature. This study presents a machine learning approach that reconstructs NACs from a set of auxiliary single-valued functions.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Bing Gu, Shaul Mukamel
Summary: The singlet fission process in pentacene dimers mediated by a conical intersection can be controlled by coupling the molecule to a confined optical cavity photon mode, leading to significant suppression of singlet fission.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Multidisciplinary Sciences
Umberto Raucci, Hayley Weir, Christoph Bannwarth, David M. Sanchez, Todd J. Martinez
Summary: In this study, the authors used non-adiabatic first principles molecular dynamics to demonstrate the conversion of an achiral molecule to a chiral one upon photoexcitation, highlighting the possibility of asymmetric photochemistry starting from achiral reactants.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shutaro Karashima, Xincheng Miao, Akio Kanayama, Yo-ichi Yamamoto, Junichi Nishitani, Nikita Kavka, Roland Mitric, Toshinori Suzuki
Summary: In this study, we discovered the ultrafast ring closure reaction of gaseous cis-St for the first time using extreme ultraviolet time-resolved photoelectron spectroscopy. Previous computational simulations predicted a quantum yield of only 0.04 for the formation of 4a,4b-dihydrophenanthrene (DHP) from cis-St, but our results showed a different branching ratio of 0.55:0.41:0.04 for cis-St:DHP:trans-St.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Daeheum Cho, Bing Gu, Shaul Mukamel
Summary: Optical cavities provide a versatile platform for manipulating the excited-state dynamics of molecules. The study observes a novel polaritonic conical intersection (PCI) and finds that it can significantly change the nonadiabatic dynamics of molecules. Additionally, the absorption spectrum and excited-state dynamics can be systematically manipulated by adjusting the parameters of the optical cavity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Qianqian Gong, Yazhen Li, Xiaoke Nie, Fengyi Liu
Summary: The multilevel ONIOM framework has been proven to be an efficient tool for understanding the mechanism of aggregation-induced emission (AIE). The ionic styryl-pyridine salt (SPH) has been identified as a new class of AIEgen with high fluorescence yield. Choosing the appropriate QM model (monomer or dimer) is crucial for studying the AIE mechanism of SPH. The dimer model provides increased barriers and a red-shifted emission wavelength, while also revealing the exciton coupling in the fluorescence emission state.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Thomas Schaupp, Volker Engel
Summary: This study investigates the three-dimensional correlated motion of an electron and a proton. The dynamics in the electronic ground state is well described by the Born-Oppenheimer approximation, while in the first excited electronic state, the nuclear wave packet motion takes place through a ring of conical intersections accompanied by effective population transfer. The total nuclear probability and flux densities resemble those obtained for the ground state dynamics, indicating that the wave packet dynamics in three-dimensional space does not exhibit features of non-adiabatic dynamics.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Dong Yang, Larissa K. S. Krbek, Le Yu, Tanya K. Ronson, John D. Thoburn, John P. Carpenter, Jake L. Greenfield, Duncan J. Howe, Biao Wu, Jonathan R. Nitschke
Summary: By assembling a specific metal-organic structure, the library can dynamically adjust its structure and function in response, achieving selective binding of monosaccharides and promoting mutarotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Analytical
Yujia Liu, Yibing Li, Le Yu, Zhaoyi Yang, Ju Ding, Kang-Nan Wang, Yanrong Zhang
Summary: A multifunctional photosensitizer was designed to be specifically activated by inflammatory cytokines and tumor markers, releasing a ratiometric fluorescence signal. This novel strategy showed promising results in the treatment of inflammation-associated tumors.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Chaochao Fan, Yue Wang, Jie Zhao, Yanxia Zhao, Dong Yang, Boyang Li, Le Yu, Xiao-Juan Yang, Biao Wu
Summary: In this study, two photoactive ligands were designed and used to construct sulfate complexes. These complexes can undergo oxygenation reactions under light, storing singlet oxygen, and partially recover the original structures after heating.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Isabelle Weber, Chen-Wen Wang, Shang-Chen Huang, Chao-Yuan Zhu, Yuan-Pern Lee
Summary: Matrix isolation spectroscopy with para-hydrogen (p-H2) was used to study the electronic transitions of the 1-hydronaphthyl radical (1-C10H9) isolated in solid p-H2. The dispersed fluorescence and fluorescence excitation spectra were observed, and vibronic transitions were assigned through comparison with simulated spectra. The fluorescence spectrum complemented the infrared spectrum and provided additional vibrational mode information, while the excitation spectrum covered a wider spectral range. Comparison with spectra from different matrices helped evaluate the influence of p-H2 as a matrix host on the electronic transition of 1-C10H9 and discuss its potential contribution to diffuse interstellar bands.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Review
Chemistry, Multidisciplinary
Chaoyuan Zhu
Summary: In this paper, damped harmonic oscillators that consider local-mode nuclear vibrations interacting with solvent molecules are developed into Franck-Condon factors. By scaling an unperturbed Hessian matrix and diagonalizing the perturbed Hessian matrix, the Huang-Rhys factors can be directly modified to reproduce solvent-enhanced absorption and fluorescence spectra of solute molecules.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Ying Zhang, Le Yu, Xu-Dong Zhang, Ya-Hui Wang, Chunpeng Yang, Xiaolong Liu, Wen-Peng Wang, Yu Zhang, Xue-Ting Li, Ge Li, Sen Xin, Yu-Guo Guo, Chunli Bai
Summary: By incorporating phosphorus-containing functional groups into a hydrocarbon-based polymer, a smart risk-responding polymer is developed to effectively mitigate battery thermal runaway. The polymer is (electro)chemically compatible with electrodes at room temperature, ensuring stable battery operation. The phosphorus-containing radicals dissociate from the polymer and scavenge hydrogen and hydroxyl radicals, suppressing thermal generation and extending the time before thermal runaway, creating a critical time window for safety management.
Article
Chemistry, Multidisciplinary
Xin Pan, Yajie Lu, Weixing Zhou, Wenyu Zhang, Ling Yang, Chaoyuan Zhu, Sheng-Hsien Lin
Summary: Since the proposal of the concept of aggregation-induced emission (AIE) in 2001, the exploration of AIE mechanism and the development of high-performance AIE materials have become the central focus of this field. Through extensive experiments, AIE mechanism has been well explained, such as restricted intramolecular motion (RIM) and J-aggregates. Tetraphenylethlene (TPE) molecules exhibit AIE effect due to the blocking of benzene ring rotor rotation and subsequent release of energy as radiation when stacked. This study investigates the AIE effect of TPE-an monomer and dimer through electronic structure calculations, spectrum simulation, and AIE mechanism calculations in different solvents. The results demonstrate that aggregation leads to enhanced fluorescence intensity by altering the molecular structure, thereby providing theoretical guidance for the design of AIE materials.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Binglian Yang, Wuping Xue, Baoqing Yu, Huailin Pang, Le Yu, Qingling Wang, Dianhu Zhu
Summary: A novel method for the synthesis of Azoxystrobin using trimethylamine as a catalyst is reported in this study. The catalytic system offers several advantages including low cost, excellent reactivity, easy recovery, and minimal environmental impact. Mechanistic studies and DFT calculations suggest that the involvement of a highly active quaternary ammonium salt intermediate is responsible for the efficient catalysis.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Physical
Yilong Li, Lulu Liu, Dingjian Shan, Fangcan Liang, Shuo Wang, Le Yu, Ji-Quan Liu, Qingling Wang, Xinxin Shao, Dianhu Zhu
Summary: This study reports a novel synthetic method for the reductive coupling of organic halides with in situ-generated sulfinyl sulfones using a nickel catalyst and zinc reductant. The reaction exhibits broad substrate applicability and good functional group tolerance, making it suitable for the synthesis of complex organic molecules and thioether-containing drugs.
Article
Chemistry, Physical
Yazhen Li, Chaoyuan Zhu, Fenglong Gu, Fengyi Liu
Summary: In this study, the photocyclization mechanism of donor-acceptor Stenhouse adducts (DASA) was revealed through calculations. It was found that the thermal-then-photo isomerization channel EEZ -EZZ -EZE is dominant, instead of the commonly accepted EEZ -EEE -EZE channel, and a competitive stepwise channel was proposed for the final ring-closure step. These findings redraw the mechanistic picture of the DASA reaction and provide critical physical insight into the interplay between thermal-and photo-induced processes in photochemical synthesis and reactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Nanoscience & Nanotechnology
Haojie Wang, Yuan Wang, Wenhua Xu, Haixin Zhang, Jinmeng Lv, Xue Wang, Zhi Zheng, Yanxia Zhao, Le Yu, Quan Yuan, Leixiao Yu, Bo Zheng, Lingyan Gao
Summary: This study demonstrates the modulation of guest reactivity within a macrocyclic cavity using pillar[5]arene, which enhances guest photoactivity and nitric oxide generation. The system shows broad-spectrum antibacterial activity and promotes wound healing.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
He Wang, Tianhe Yang, Yuechun Li, Le Yu, Yibo Lei, Chaoyuan Zhu
Summary: Nonadiabatic molecular dynamics simulations have been performed to study the ultrafast photo-induced ring-opening and isomerization reactions of 2,2-diphenyl-2H-chromene (DPC) upon S1 excitation. The simulations reveal that the DPC-T and DPC-C conformers exhibit different efficiencies and rates of ring-opening, in agreement with experimental observations. This study provides valuable insights into the photorelaxation mechanisms of DPC and the development of photoresponsive materials.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yu-Hui Liu, Shi-Bo Yu, Ya-Jing Peng, Chen-Wen Wang, Chaoyuan Zhu, Sheng-Hsien Lin
Summary: This study investigated the ESIPT reaction of two phenol-quinoline molecules using time-dependent density functional theory. The different carbocycle structures between the molecules were found to affect the reaction rate and barrier. Vibrational excitation played a key role in lowering the reaction barrier.
Article
Chemistry, Multidisciplinary
Qing Zhang, Yuanyuan Li, Zexing Cao, Chaoyuan Zhu
Summary: This study investigates the aggregation-induced emission (AIE) spectra of two triphenylamine salicylaldehyde derivatives through molecular simulations, revealing the mechanisms associated with excited state intramolecular proton transfer (ESIPT) and intermolecular charge-transfer. The simulation results are in good agreement with experimental data, providing insights into the design of highly efficient AIE compounds.
Article
Chemistry, Physical
Ying Hu, Ling Yue, Feng Long Gu, Chaoyuan Zhu
Summary: By performing global-switching on-the-fly trajectory surface-hopping molecular dynamics simulation at the OM2/MRCI quantum level, the study probed the S-3(pi pi*) photoisomerization mechanisms associated with excited-state intramolecular hydrogen transfer for 2'-hydroxychalcone (2HC). The simulation found that the quantum yields of cis-to-trans and trans-to-cis photoisomerization were low due to the conical intersections being localized in either the cis-2HC or trans-2HC region, suggesting potential strategies to enhance the quantum yield of 2HC photoisomerization by suppressing hydrogen transfer and shifting conical intersections.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
