The Journal of Physical Chemistry Letters最新文献_第7页

Spin Mixing in Intramolecular Singlet Fission: A First-Principles-Based Quantum Dynamical Study 分子内单子裂变中的自旋混合：基于第一原理的量子动力学研究

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02794

R. K. Kathir, Pedro B. Coto, Michael Thoss

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Cooperative and Local Molecular Motion of High-Density Water in Glycerol Aqueous Solutions 甘油水溶液中高密度水的协同和局部分子运动

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02462

Kaito Sasaki, Yoshiharu Suzuki

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Resonant Vibrational Enhancement of Downhill Energy Transfer in the C-Phycocyanin Chromophore Dimer C-Phycocyanin 色素二聚体中下坡能量转移的共振振动增强

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02386

Siddhartha Sohoni, Ping-Jui Eric Wu, Qijie Shen, Lawson T. Lloyd, Craig MacGregor-Chatwin, Andrew Hitchcock, Gregory S. Engel

{"title":"Resonant Vibrational Enhancement of Downhill Energy Transfer in the C-Phycocyanin Chromophore Dimer","authors":"Siddhartha Sohoni, Ping-Jui Eric Wu, Qijie Shen, Lawson T. Lloyd, Craig MacGregor-Chatwin, Andrew Hitchcock, Gregory S. Engel","doi":"10.1021/acs.jpclett.4c02386","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02386","url":null,"abstract":"Energy transfer between electronically coupled photosynthetic light-harvesting antenna pigments is frequently assisted by protein and chromophore nuclear motion. This energy transfer mechanism usually occurs in the weak or intermediate system-bath coupling regime. Redfield theory is frequently used to describe the energy transfer in this regime. Spectral densities describe vibronic coupling in visible transitions of the chromophores and govern energy transfer in the Redfield mechanism. In this work, we perform finely sampled broadband pump–probe spectroscopy on the phycobilisome antenna complex with sub-10-fs pump and probe pulses. The spectral density obtained by Fourier transforming the pump–probe time-domain signal is used to perform modified Redfield rate calculations to check for vibrational enhancement of energy transfer in a coupled chromophore dimer in the C-phycocyanin protein of the phycobilisome antenna. We find two low-frequency vibrations to be in near-resonance with the interexcitonic energy gap and a few-fold enhancement in the interexcitonic energy transfer rate due to these resonances at room temperature. Our observations and calculations explain the fast downhill energy transfer process in C-phycocyanin. We also observe high-frequency vibrations involving chromophore–protein residue interactions in the excited state of the phycocyanobilin chromophore. We suggest that these vibrations lock the chromophore nuclear configuration of the excited state and prevent the energetic relaxation that blocks energy transfer.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Thermoelectric Properties of Benzothieno-Benzothiophene Self-Assembled Monolayers in Molecular Junctions 分子结中苯并噻吩-苯并噻吩自组装单层的热电特性

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02753

Sergio Gonzalez-Casal, Rémy Jouclas, Imane Arbouch, Yves Henri Geerts, Colin van Dyck, Jérôme Cornil, Dominique Vuillaume

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Superior Photostability of the Unnatural Base 6-Amino-5-nitropyridin-2-ol: A Case Study Using Ultrafast Broadband Fluorescence, Transient Absorption, and Theoretical Computation 非天然碱 6-氨基-5-硝基吡啶-2-醇的卓越光稳定性：利用超快宽带荧光、瞬态吸收和理论计算进行的案例研究

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02751

Qingwu Xiong, Ping Wang, Chensheng Ma, Alvis Tsz-Kit Law, Mingliang Wang, Wai-Ming Kwok

{"title":"Superior Photostability of the Unnatural Base 6-Amino-5-nitropyridin-2-ol: A Case Study Using Ultrafast Broadband Fluorescence, Transient Absorption, and Theoretical Computation","authors":"Qingwu Xiong, Ping Wang, Chensheng Ma, Alvis Tsz-Kit Law, Mingliang Wang, Wai-Ming Kwok","doi":"10.1021/acs.jpclett.4c02751","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02751","url":null,"abstract":"6-Amino-5-nitropyridin-2-ol (Z), a nitroaromatic compound and a base for Hachimoji nucleic acids, holds significant potential in expanding the genetic alphabet, as well as in synthetic biology and biotechnology. Despite its promising applications, the spectral characterization and photoinduced properties of Z have remained largely unexplored until now. This study presents a comprehensive investigation into its excited state dynamics in various solvents, utilizing state-of-the-art ultrafast broadband time-resolved fluorescence and transient absorption spectroscopy, complemented by computational methods. The acquired results provide direct experimental evidence that, upon photoexcitation, Z emits prompt fluorescence from a nearly planar structure in its excited state, independent of solvent properties. This state deactivates nonradiatively within sub-picoseconds through internal conversion with a unitary yield, primarily mediated by the rotation of the nitro group. This unusually rapid deactivation pathway entirely excludes the involvement of long-lived nπ* states, triplet states, and photoproducts, which are commonly observed in most nitroaromatic compounds and natural DNA and RNA bases. Our findings underscore that Z, as an unnatural base, exhibits superior photostability compared to canonical natural bases. This provides valuable insights into the photodynamics of nitroaromatic compounds, which is beneficial for strategic substitution design in environmental and biological applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"155 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Tracking the Facet Transformation of CeO2 by 17O Solid-State Nuclear Magnetic Resonance 通过 17O 固态核磁共振追踪 CeO2 的面转变

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02615

Yujie Wen, Wenjing Zhang, Juan Wen, Fang Wang, Xiaokang Ke, Junchao Chen, Luming Peng

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Silver Electrodes Are Highly Selective for CO in CO2 Electroreduction due to Interplay between Voltage Dependent Kinetics and Thermodynamics 银电极在二氧化碳电还原过程中对一氧化碳的高选择性源于电压相关动力学和热力学之间的相互作用

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02869

Michele Re Fiorentin, Francesca Risplendi, Clara Salvini, Juqin Zeng, Giancarlo Cicero, Hannes Jónsson

{"title":"Silver Electrodes Are Highly Selective for CO in CO2 Electroreduction due to Interplay between Voltage Dependent Kinetics and Thermodynamics","authors":"Michele Re Fiorentin, Francesca Risplendi, Clara Salvini, Juqin Zeng, Giancarlo Cicero, Hannes Jónsson","doi":"10.1021/acs.jpclett.4c02869","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02869","url":null,"abstract":"Electrochemical reduction is a promising way to make use of CO2 as feedstock for generating renewable fuel and valuable chemicals. Several metals can be used as the electrocatalyst to generate CO and formic acid, but hydrogen formation is an unwanted side reaction that can even be dominant. The lack of selectivity is, in general, a significant problem, but silver-based electrocatalysts have been shown to be highly selective, with faradaic efficiency of CO production exceeding 90%, when the applied voltage is below −1 V vs RHE. In this voltage range, only a small amount of hydrogen and formate is formed. We present calculations of the activation free energy for the various elementary steps as a function of applied voltage at the three low index facets, Ag(111), Ag(100) and Ag(110), as well as experimental measurements on polycrystalline electrodes, to identify the reason for this high selectivity. The formation of formic acid is suppressed, even though it is thermodynamically favored, because of the low coverage of adsorbed hydrogen and kinetic hindrance to the formation of the HCOO* intermediate, while *COOH, a key intermediate in CO formation, is thermodynamically unstable until the applied voltage reaches −1 V vs RHE, at which point the kinetics for its formation are more favorable than for hydrogen. The calculated results are consistent with experimental measurements carried out for acidic conditions and provide an atomic scale insight into the high CO selectivity of silver-based electrocatalysts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"1 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Vibrational Relaxation Completes the Excitation Energy Transfer and Localization of Vibronic Excitons in Allophycocyanin α84-β84 振动弛豫完成异叶花青素 α84-β84 中振动激子的激发能量转移和定位

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02387

Ping-Jui Eric Wu, Siddhartha Sohoni, Gregory S. Engel

{"title":"Vibrational Relaxation Completes the Excitation Energy Transfer and Localization of Vibronic Excitons in Allophycocyanin α84-β84","authors":"Ping-Jui Eric Wu, Siddhartha Sohoni, Gregory S. Engel","doi":"10.1021/acs.jpclett.4c02387","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02387","url":null,"abstract":"Phycobilisomes are light-harvesting complexes that play a key role in photosynthesis in cyanobacteria, which generate more than 40% of the world’s oxygen. The near-unity excitation energy transfer efficiency from phycobilisomes to photosystems highlights its importance in understanding efficient energy transfer processes. Spectroscopic studies have shown that the 280 fs rapid excitonic downhill energy transfer within the α84-β84 chromophore dimer in allophycocyanin (APC), a subunit of phycobilisomes, is crucial to this efficiency. However, the role of strong chromophore–protein interactions and vibrational relaxation requires further exploration to fully explain this efficient downhill energy transfer. A theory is required that adequately describes exciton dynamics in an intermediate region while also incorporating vibrational relaxation mediated by protein bath modes. In this work, we incorporate vibrational relaxation into modified Redfield theory by introducing coupling fluctuation. We holistically simulate the rapid excitation energy transfer process of the α84-β84 chromophore dimer in APC and successfully model the recently observed rapid energy capture. We find that vibrational relaxation dictates capture of excitons by the localized state of the β84 chromophore. The calculated rate shows excellent agreement with previous ultrafast spectroscopic experiments. Our results show that the inclusion of vibrational relaxation is essential for systems that utilize vibronic coupling to enhance energy transfer and capture. Consequently, incorporating vibrational relaxation into Modified Redfield theory shows promise for accurately describing the excitation energy transfer process in other photosynthetic systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"2 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Origin of Intrinsically Low Lattice Thermal Conductivity in Solids 固体本征低晶格导热性的起源

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-11 DOI: 10.1021/acs.jpclett.4c02770

Yu Wu, Anqi Huang, Linxuan Ji, Jialin Ji, Yimin Ding, Liujiang Zhou

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Overtone Excitation of Nitrogen Molecules via Stimulated Raman Pumping 通过受激拉曼泵浦实现氮分子的泛音激发

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-10 DOI: 10.1021/acs.jpclett.4c02608

Yue Xiao, Liping Wen, Zhichao Li, Jie Han, Wenjie Wu, Tao Wang, Yurun Xie, Tiangang Yang

{"title":"Overtone Excitation of Nitrogen Molecules via Stimulated Raman Pumping","authors":"Yue Xiao, Liping Wen, Zhichao Li, Jie Han, Wenjie Wu, Tao Wang, Yurun Xie, Tiangang Yang","doi":"10.1021/acs.jpclett.4c02608","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02608","url":null,"abstract":"Nitrogen bond activation is a pivotal process in chemistry, with bond excitation being fundamental to understanding the underlying mechanisms, making the preparation of molecules in specific quantum states crucial. Here we report the first overtone excitation of the N2 molecule from X1Σg+(v = 0, j = 0, 1, and 2) to X1Σg+(v = 2, j = 0, 1, 2, and 3) using the stimulated Raman pumping (SRP) method in a pulsed molecular beam. N2 was detected using 2+1 resonance-enhanced multiphoton ionization through the a″1Σg+ state. An excitation efficiency of 4% was achieved within the excitation region in which the SRP laser intensity was saturated, indicating the low cross-sectional nature of the process. The SRP detuning spectra for different branches were measured, and the excited N2 [X1Σg+(v = 2)] was further used to access various vibrational states of a″1Σg+, enabling the determination of its vibrational constants. This research opens up new opportunities for studying the specific high vibrational excitation of nitrogen in reactions and scattering experiments and contributes additional precise spectral data for the N2 molecule.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"196 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0