Article
Chemistry, Physical
Saniya Gratious, Akhil S. Nair, Sayani Mukherjee, Neha Kachappilly, Biswarup Pathak, Sukhendu Mandal
Summary: Understanding the structural growth patterns and property evolution in nanoclusters is crucial for designing clusters with specific properties. The transformation of Au-44(SPh-Bu-t)(28) to Au-36(SPh-Bu-t)(24) through deassembly of an Au-8(SPh-Bu-t)(4)d fragment was found to follow zero-order kinetics with low activation energy, with surface restructuring identified as the rate-determining step. Proposed mechanistic pathway offers insights into nanocluster structure evolution.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Review
Chemistry, Physical
Meng Zhou, Rongchao Jin
Summary: This review summarizes recent progress in the excited-state dynamics of atomically precise gold nanoclusters, discussing their electronic structure, relaxation pathways, and dynamics dependent on size, shape, structure, and composition. Quantum confinement effects, size dependence in exciton and electron dynamics, and the role of coherent oscillations in excited-state relaxation are also explored. The review provides insights into future directions in this area.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 72
(2021)
Article
Chemistry, Physical
Jacob M. Garcia, Lauren F. Heald, Ryan E. Shaffer, Scott G. Sayres
Summary: Researchers found that the excited state lifetimes of neutral titanium oxide clusters are correlated with the size and structural rigidity of the clusters, with clusters possessing structural rigidity showing longer excited state lifetimes.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Wataru Ishii, Yoshinori Okayasu, Yoichi Kobayashi, Rika Tanaka, Shohei Katao, Yoshiko Nishikawa, Takuya Nakashima, Tsuyoshi Kawai
Summary: The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. The modification of trianionic [Ag29(BDT)12(TPP)4]3- NC with silver(I) complexes led to intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag29 NC is confirmed by various measurements, and the change in excited-state dynamics by the binding is discussed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Junichi Okamoto, Francesco Peronaci
Summary: The study focuses on the properties of Floquet prethermal states in two-dimensional Mott-insulating Hubbard clusters under continuous optical excitation. It was found that Floquet prethermal states not only emerge off resonance, but also for resonant excitation with a small field amplitude. The long-lived quasi-stationary Floquet states in the resonant case are characterized by Rabi oscillations, while at stronger fields, thermalization to infinite temperature is observed. The results are explained using time-dependent perturbation theory and substantiated by finite-size analysis.
SCIENTIFIC REPORTS
(2021)
Article
Materials Science, Multidisciplinary
Quan-Li Shen, Long-Yun Shen, Le-Yi Chen, Lu-Bing Qin, Yong-Gang Liu, Nicholas M. Bedford, Francesco Ciucci, Zheng-Hua Tang
Summary: A systematic study is reported to examine the enhanced oxygen evolution reaction (OER) performance of NiFe layered double hydroxides (NiFe-LDHs) by loading atom-precise all alkynyl-protected [Au-28((BuC)-Bu-t equivalent to C)(17)](-) nanoclusters on their surface. The loaded Au nanoclusters exhibit a significantly lower overpotential and Tafel slope compared to thiolate-protected Au-28(TBBT)(20) nanoclusters, indicating improved electrocatalytic activity. This enhanced performance is attributed to the interfaces created between NiFe-LDHs and Au nanoclusters, leading to more significant charge transfer and a lower energy barrier for the potential-determining step in the OER process.
Article
Chemistry, Multidisciplinary
Svetlana Shostak, Woojin Park, Juwon Oh, Jinseok Kim, Seunghoon Lee, Hyeongwoo Nam, Michael Filatov, Dongho Kim, Cheol Ho Choi
Summary: The excited-state aromatization dynamics in the photochemical ring opening of DHA was investigated using nonadiabatic molecular dynamics simulations and the mixed-reference spin-flip (MRSF)-TDDFT method. It was found that the ring opening occurs in the excited state through a series of steps with increasing aromaticity. The competition between Baird and anti-Baird channels suggests that the quantum yield of the photochemical products can be controlled by tipping their balance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Victor M. Freixas, Alexander J. White, Tammie Nelson, Huajing Song, Dmitry Makhov, Dmitrii Shalashilin, Sebastian Fernandez-Alberti, Sergei Tretiale
Summary: This study compares three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). The comparisons reveal method performance for population relaxation and coherent vibronic dynamics. The numerical convergence of MCE-AIMC algorithms is also studied to provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Physics, Multidisciplinary
Angel L. Corps, Armando Relano
Summary: This study discusses a broad class of excited-state quantum phase transitions that lead to two different excited-state quantum phases, where equilibrium expectation values crucially depend on a specific conserved quantity in one phase, while energy is the only relevant thermodynamic magnitude in the other phase. The operator in the first phase acts as a discrete symmetry with two different eigenvalues.
PHYSICAL REVIEW LETTERS
(2021)
Article
Chemistry, Physical
Lixin Yang, Qiuyi He, Wenhua Han, Pengye Liu, Wen Wu Xu
Summary: The application of grand unified model and ring model in understanding the isomeric structures of six Au-28(SR)(20) nanoclusters reveals that the structural isomerism can be understood by different types of ring structures packing, fusing, or interlocking together.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Astronomy & Astrophysics
Wei Chao, Jing-Jing Feng, Mingjie Jin
Summary: In this paper, the impact of the decay of excited states on the effective number of neutrino species, Neff, is investigated in the framework of pseudo-Dirac cold dark matter via the Higgs portal. The relic density and direct detection signal of the dark matter are calculated, revealing the available parameter space. The study shows that the decay of excited states can lead to a maximum value of j Delta Neffj of the order Oo0.1 thorn, which can be probed by future CMB-S4 and SPT/SO projects.
Article
Chemistry, Multidisciplinary
Srestha Basu, Hussein Fakhouri, Christophe Moulin, Santanu Dolai, Isabelle Russier-Antoine, Pierre-Francois Brevet, Rodolphe Antoine, Anumita Paul
Summary: This study reports the unprecedented determination of the molar mass of zinc-mediated assemblies of homoleptic gold nanoclusters using charge detection mass spectrometry measurements, which further allows the accurate determination of the two-photon excited photoluminescence cross section. The observation of a four orders-of-magnitude enhancement in two-photon excited photoluminescence of gold nanoclusters following complexation with zinc ions not only deepens the fundamental understanding of the properties of atomic clusters under multiphoton excitation, but also expands their potential applications as luminescent markers.
Article
Chemistry, Physical
Junsheng Chen, Ajeet Kumar, Cecilia Cerretani, Tom Vosch, Donatas Zigmantas, Erling Thyrhaug
Summary: Due to desirable optical properties, such as efficient luminescence and large Stokes shift, DNA-templated silver nanoclusters (DNA-AgNCs) have received significant attention over the past decade. In this study, we investigate the early time relaxation dynamics of a 16-atom silver cluster (DNA-Ag16NC) with NIR emission and an unusually large Stokes shift. By using ultrafast optical spectroscopy, we extract a kinetic model to clarify the physical picture of the photoinduced dynamics, which can guide further research on the electronic structure and dynamics of these novel objects and their potential applications.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Victor Manuel Freixas, Sergei Tretiak, Sebastian Fernandez-Alberti
Summary: Progress in organic synthesis allows the exploration of diverse molecules with new structural topologies. The recently synthesized infinitene is a helically twisted figure-eight molecule with unique optoelectronic properties suitable for applications in nanoelectronics and photonics. However, the photophysical properties of infinitene have not been investigated.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Optics
Zhen-Xia Niu, Qian Wang
Summary: In this work, the dynamical characteristics of excited-state quantum phase transitions (ESQPTs) in a spin-1 Bose-Einstein condensate (BEC) are investigated using the Loschmidt echo spectrum. The study reveals a significant change in the Loschmidt echo spectrum near the critical point of the ESQPT, and the spectrum exhibits a particular behavior at the critical point, serving as a dynamical detector for probing the ESQPT. Furthermore, the energy distribution associated with the Loschmidt echo spectrum is demonstrated to capture the features of the ESQPT in both time-evolved and long-time-averaged cases.
Article
Chemistry, Multidisciplinary
Kaia. R. R. Parenti, Rafi Chesler, Guiying He, Pritam Bhattacharyya, Beibei Xiao, Huaxi Huang, Daniel Malinowski, Jocelyn Zhang, Xiaodong Yin, Alok Shukla, Sumit Mazumdar, Matthew. Y. Y. Sfeir, Luis. M. M. Campos
Summary: Quantum interference is crucial in organic molecular electronics and can be predicted using graphical models. In this study, we investigated its application in intramolecular singlet-fission compounds and found that destructive interference leads to slower triplet pair formation.
Article
Instruments & Instrumentation
Siedah J. Hall, Peter J. Budden, Anne Zats, Matthew Y. Sfeir
Summary: A major limitation of transient optical spectroscopy is the need for relatively high laser fluences to achieve broadband, multichannel detection with acceptable signal-to-noise levels. However, new opportunities have emerged with the proliferation of commercial laser systems offering high repetition rates and high pulse energies, allowing high sensitivity pump-probe measurements at low pump fluences. In this study, a high repetition rate, broadband transient spectrometer capable of multichannel shot-to-shot detection at 90 kHz was demonstrated. By using a modified modulation and data processing scheme, a noise level of 10(-5) in 4 s for differential transmission was achieved, enabling measurement of signals on the order of 10(-6) OD for low-dimensional materials.
REVIEW OF SCIENTIFIC INSTRUMENTS
(2023)
Article
Multidisciplinary Sciences
Wei -Dan Si, Chengkai Zhang, Meng Zhou, Wei-Dong Tian, Zhi Wang, Qingsong Hu, Ke-Peng Song, Lei Feng, Xian-Qiang Huang, Zhi-Yong Gao, Chen-Ho Tung, Di Sun
Summary: In this study, an all-alkynyl-protected gold nanocluster, Au20, with distinguished photophysical properties including near-infrared dual-emission (DE) at 820 and 940 nm and high photo-luminescent quantum yield, was synthesized. Through systematic spectroscopic and theoretical studies, two triplet charge transfer states, ligand-to-kernel and kernel-based CT states, were identified as the origins of DE. The NIR DE also exhibited highly independent and sensitive responses to surrounding environments. This work provides insights into the DE mechanism and promotes the development of NIR DE materials.
Article
Chemistry, Multidisciplinary
Wei Zhang, Jie Kong, Rong Miao, Hongwei Song, Yalei Ma, Meng Zhou, Yu Fang
Summary: A molecular engineering strategy is developed to achieve fluorescent chromophores with integrated AIE and TICT properties. The TICT properties are validated through theoretical calculations and experimental techniques. The findings provide mechanistic elucidation for the design of chromophores with high tunability and strong emissions.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Kenji Iida, Takashi Takeuchi, Ryota Katsumi, Takashi Yatsui
Summary: We performed first-principles calculations to investigate the optical response of an Au147azobenzene complex and found that the interfacial contact between Au147 and azobenzene plays a significant role in modulating the optical properties of azobenzene. The absorption of isolated azobenzene weakens with an increase in the Au147-azobenzene interaction, while the absorption measured with light field along the Au147-azobenzene alignment strengthens. The charge-transfer excitation mechanism between Au147 and azobenzene also changes remarkably depending on the strength of the interfacial interaction.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Siyu Xie, Lin Ma, Teng-Fei Xiao, Jiawen Zhang, Jie Kong, Zhuoran Kuang, Meng Zhou, Guo-Qiang Xu, Yang Li, Andong Xia
Summary: The excited-state dynamics of an organic dyad (Cz-NI) were studied in different polar solvents. The formation of an intramolecular charge separation (ICS) state with twisted structure in polar solvents was found, driven and stabilized by solvation dynamics. Orbital decoupling, intramolecular torsional motion, and transition moments associated with ICT emission were identified as factors limiting excited-state deactivation. The orthogonal pi-system of the ICS state enables efficient spin-orbit and charge-transfer transitions to a triplet state with long lifetime and high reduction potential for subsequent reactions.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Yan-zhen Wu, Jie Kong, Wei Zhang, Shuxin Wang, Meng Zhou
Summary: Doping and alloying are effective strategies to improve the performance of metal nanoclusters, while the effect of foreign atoms on the mechanical properties of metal nanoclusters remains largely unknown. In this study, we investigated the effect of silver alloying on the mechanical properties of rod-shaped gold nanoclusters. Our results provide new insights into the photophysics of alloy metal nanoclusters.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Zhongyu Liu, Meng Zhou, Lianshun Luo, Yitong Wang, Ellen Kahng, Rongchao Jin
Summary: Research on the photoluminescence (PL) of classic Au-25(SR)(18) and its doped nanoclusters (NCs) has left many questions unanswered due to complex electron dynamics. This study focuses on the homogold Au-25 and doped NCs, as well as Ag-25 and doped ones, to understand the influencing factors and elucidate the PL mechanism. The strong electron-vibration coupling in Au-25 leads to weak PL, while Cd or Hg doping strengthens the coupling with staple vibrations but reduces the coupling with core breathing and quadrupolar modes. On the other hand, weaker electron-vibration coupling in Ag-25 results in higher PL, and Au doping further enhances the radiative rate and suppresses nonradiative decay rate in AuAg24. However, excessive Au doping triggers strong electron-vibration coupling, counteracting the radiative enhancement effect.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Thomas S. C. MacDonald, Murad J. Y. Tayebjee, Miles I. Collins, Elango Kumarasamy, Samuel N. Sanders, Matthew Y. Sfeir, Luis M. Campos, Dane R. McCamey
Summary: In this report, the use of continuous-wave and pulsed electron spin resonance techniques to study the properties of triplet-pair states is demonstrated. It is found that the generation rate of high-spin triplet pairs is dependent on the molecular orientation and the static magnetic field. This finding is important for materials design and applications in photovoltaics, information technologies, and biomedical imaging.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Guiying He, Emily M. Churchill, Kaia R. Parenti, Jocelyn Zhang, Pournima Narayanan, Faridah Namata, Michael Malkoch, Daniel N. Congreve, Angelo Cacciuto, Matthew Y. Sfeir, Luis M. Campos
Summary: Singlet fission and triplet-triplet annihilation upconversion are two closely related multiexciton processes. The authors introduce a series of dendritic macromolecules to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation. This study sheds light on the impact of multiexcitonic through-space interactions in macromolecular architectures.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Along Ma, Jiawei Wang, Jie Kong, Yonggang Ren, Yuxuan Wang, Xiaoshuang Ma, Meng Zhou, Shuxin Wang
Summary: The synthesis, structure determination, and photoluminescence of Au10Ag17 and Au12Ag13 nanoclusters were reported. Au10Ag17 exhibited a low photoluminescence quantum yield, while the removal of two terminal silver atoms led to a 15-fold increase in photoluminescence. The discovery of such a photoluminescence switch provides an interesting opportunity to understand the origin of fluorescence in nanoclusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Takahiro Chiba, Kenji Iida, Shinya Furukawa, Jun-ya Hasegawa
Summary: The study investigates the effect of electric fields on hydrogen or proton transfer through hydroxyl groups on an anatase TiO2 (101) surface using first-principles density functional theory and the modern theory of polarization. Unidirectional surface proton transfer induced by external electric fields at different orientations towards the surface is the focus of this research. The preferred pathway for proton transfer can change depending on the magnitude and direction of the electric field. Detailed analysis reveals that the variation in the energy profile with the electric field is significantly different from the classical electric work of an electric field carrying a point charge. The electric field effect on the energy profile of proton transfer is governed by the rearrangement of the chemical bond network at the interface between water molecules and the surface.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Grayson Johnson, Moon Young Yang, Chang Liu, Hua Zhou, Xiaobing Zuo, Diane A. Dickie, Sihan Wang, Wenpei Gao, Bukuru Anaclet, Frederic A. Perras, Fuyan Ma, Chenjie Zeng, Da Wang, Sara Bals, Sheng Dai, Zhen Xu, Guoliang Liu, William A. Goddard III, Sen Zhang
Summary: A scalable and generalized approach to synthesizing superstructures assembled from atomically precise nanoclusters has been reported, with a detailed description of the self-assembly mechanism. The chemical tuning of surface ligands controls superstructure disassembly and reassembly, enabling the synthesis of multicomponent superstructures. This research is promising for the preparation of superstructures for use in electronics, plasmonics, magnetics, and catalysis.
Article
Chemistry, Multidisciplinary
Wei Zhang, Jie Kong, Yingwei Li, Zhuoran Kuang, He Wang, Meng Zhou
Summary: The coherent vibrational dynamics of gold nanoclusters provide important information on the coupling between vibrations and electrons as well as their mechanical properties. The study focuses on atomically precise Au-144(SR)(60) nanoclusters and reveals distinct vibrational modes at 1.5 THz and 2 THz, which help understand the physical properties of gold nanostructures between molecular-like nanoclusters and metallic-state nanoparticles.
Article
Chemistry, Multidisciplinary
Michael P. Campos, Jonathan De Roo, Matthew W. Greenberg, Brandon M. McMurtry, Mark P. Hendricks, Ellie Bennett, Natalie Saenz, Matthew Y. Sfeir, Benjamin Abecassis, Sanjit K. Ghose, Jonathan S. Owen
Summary: A library of thio- and selenourea derivatives is used to adjust the kinetics of PbS and PbSe nanocrystal formation at various temperatures, revealing an induction delay and exploring the structure and size distribution of the nanocrystals, with results suggesting that the duration of the nucleation period has a minor influence on the size distribution.
