The Journal of Physical Chemistry Letters最新文献_第8页

The Importance of High-Frequency Modes in the Prediction of RISC Rates for TADF Molecules

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c0017610.1021/acs.jpclett.5c00176

Teodoro Pizza, Amedeo Capobianco* and Alessandro Troisi*,

{"title":"The Importance of High-Frequency Modes in the Prediction of RISC Rates for TADF Molecules","authors":"Teodoro Pizza, Amedeo Capobianco* and Alessandro Troisi*, ","doi":"10.1021/acs.jpclett.5c0017610.1021/acs.jpclett.5c00176","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00176https://doi.org/10.1021/acs.jpclett.5c00176","url":null,"abstract":"The reverse intersystem crossing (RISC) rate determines the efficiency of dyes displaying thermally activated delayed fluorescence (TADF). Such a rate can be predicted at the full quantum level by considering all the vibrational normal modes or adopting an approximated methodology which relies on single classical modes. We evaluated the importance of considering all of the vibrational degrees of freedom in computations for targeting the design of novel emissive materials from first principles. We computed the RISC rate for 17 molecules of interest for TADF by comparing a full quantum mechanics treatment based on Fermi’s golden rule with Marcus-based semiclassical approaches. The results are quantitatively and sometimes qualitatively different in the two approaches, especially when the reorganization energy is small, a common occurrence for molecules exhibiting TADF. The importance of high-frequency modes varies across the set of molecules considered, suggesting that their evaluation should become part of the molecular design process.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 12","pages":"3056–3062 3056–3062"},"PeriodicalIF":4.8,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.5c00176","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stabilization of Cu+ Sites in Cu2O-PdO Heterostructures via Orbital Engineering for Enhanced Electrochemical CO2 Reduction to Ethylene

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.4c0369710.1021/acs.jpclett.4c03697

Xiaojun Wang, Weikun Ren, Lanlan Shi, Jingxian Li, Yuanming Liu, Weijie Fu, Shiyu Wang, Shuyun Yao, Yingjie Ji, Kang Ji, Zhiyu Yang, Ningning Wu*, Xiaoxuan Wang* and Yi-Ming Yan*,

{"title":"Stabilization of Cu+ Sites in Cu2O-PdO Heterostructures via Orbital Engineering for Enhanced Electrochemical CO2 Reduction to Ethylene","authors":"Xiaojun Wang, Weikun Ren, Lanlan Shi, Jingxian Li, Yuanming Liu, Weijie Fu, Shiyu Wang, Shuyun Yao, Yingjie Ji, Kang Ji, Zhiyu Yang, Ningning Wu*, Xiaoxuan Wang* and Yi-Ming Yan*, ","doi":"10.1021/acs.jpclett.4c0369710.1021/acs.jpclett.4c03697","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03697https://doi.org/10.1021/acs.jpclett.4c03697","url":null,"abstract":"Electrochemical CO2 reduction to multicarbon products is vital for renewable fuels. While copper catalysts are effective for C2+ production, the instability of Cu+ species hinders long-term performance. The present study reports the development of a Cu2O-PdO heterojunction and investigates the influence of an unoccupied orbital energy level regulation strategy on the stabilization of interfacial crystalline Cu2O during the CO2 reduction reaction (CO2RR). The hybrid catalyst showed a significant improvement, with an 84% higher Faradaic efficiency for C2H4, and the catalyst lasted over 7 h, vastly outperforming the 2 h benchmark of Cu2O. In-situ Raman, ex-situ XRD, and theoretical calculations reveal that the broadened d-orbital in interfacial PdO provides a lower energy level for electrons, which contributes to the stabilization of adjacent Cu+ ions, and the high active interface significantly lowers the energy barrier of the CO–CO dimerization step (2*CO → *OCCO) and enhances the selectivity and activity for CO2RR to ethylene.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 12","pages":"3063–3071 3063–3071"},"PeriodicalIF":4.8,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703690","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

Coherent Spin Manipulation in Mononuclear Gadolinium-Substituted Polyoxometalate–Organic Hybrids

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c00196

Corina Rodríguez-Esteban, Estibaliz Ruiz-Bilbao, Janire Bustamante-Fernández, Floriana Tuna, Luis Lezama, Aaron Mailman, Aman Ullah, Alejandro Gaita-Ariño, Beñat Artetxe, Mathieu Gonidec, Itziar Oyarzabal

{"title":"Coherent Spin Manipulation in Mononuclear Gadolinium-Substituted Polyoxometalate–Organic Hybrids","authors":"Corina Rodríguez-Esteban, Estibaliz Ruiz-Bilbao, Janire Bustamante-Fernández, Floriana Tuna, Luis Lezama, Aaron Mailman, Aman Ullah, Alejandro Gaita-Ariño, Beñat Artetxe, Mathieu Gonidec, Itziar Oyarzabal","doi":"10.1021/acs.jpclett.5c00196","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00196","url":null,"abstract":"While most research on molecule-based electron spin qubits has focused on S = 1/2 ions for single-qubit gates, the need for qubit interactions in quantum operations has driven interest in higher-spin molecules and multilevel states. Herein, we study the spin dynamics of two mononuclear gadolinium-substituted polyoxometalate-organic hybrids with the general formula K5[Gd(α-XW11O39)(H2L)]·14H2O (X = Si, Ge; H2L = N,N′-dimethyl-N,N′-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylenediamine), 1Si-Gd and 1Ge-Gd. Pulsed EPR measurements reveal spin–lattice relaxation (T1) and quantum coherence (Tm) times of up to 2315 and 2.6 μs at 3 K, respectively, for diamagnetically diluted samples, as well as Rabi oscillations up to 20 K. The obtained results make 1Si-Gd and 1Ge-Gd two of the few Gd-based complexes displaying such behavior, highlighting the challenge of coherently manipulating the spin states of Gd. Moreover, their hybrid organic–inorganic nature endows them with chemical robustness and solution stability, essential prerequisites for surface immobilization and future integration in practical devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"22 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653824","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

Molecular Denoising Using Diffusion Models with Physics-Informed Priors

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c00274

Ishan Nadkarni, J.P. Martínez Cordeiro, Narayana R. Aluru

{"title":"Molecular Denoising Using Diffusion Models with Physics-Informed Priors","authors":"Ishan Nadkarni, J.P. Martínez Cordeiro, Narayana R. Aluru","doi":"10.1021/acs.jpclett.5c00274","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00274","url":null,"abstract":"Denoising Diffusion Probabilistic Models (DDPMs) are powerful generative models that have demonstrated superior performance in a variety of tasks and applications in material science and molecular graph modeling. Inspired by nonequilibrium statistical mechanics, these models iteratively degrade data through a forward diffusion process and then restore it by learning the time-reversal of the forward process. Despite their success, a significant drawback of DDPMs is their reliance on numerous iterations to generate high-quality samples, resulting in slow sampling. In this Letter, we introduce a strategy to improve DDPMs for atomistic systems by leveraging the thermodynamics of the data by deriving physics-informed priors. Drawing on principles from statistical mechanics, we derive physics-informed parameters for the prior distribution to initialize the Markov chain closer to the true data distribution. This strategy shortens the Markov chain, thereby improving the model’s training efficiency and accelerating the sampling process. We demonstrate the effectiveness of our method in denoising noisy radial distribution functions obtained from a single atomic configuration of diverse Lennard-Jones and multiatomic liquids.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653826","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

Anomalous Temperature-Dependent Interfacial Thermal Resistance Due to Melting

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c0011110.1021/acs.jpclett.5c00111

Yuxuan Chen, Ying Zhao*, Yi Tao, Shuo Qiao, Jun Lyu and Lin Yang*,

{"title":"Anomalous Temperature-Dependent Interfacial Thermal Resistance Due to Melting","authors":"Yuxuan Chen, Ying Zhao*, Yi Tao, Shuo Qiao, Jun Lyu and Lin Yang*, ","doi":"10.1021/acs.jpclett.5c0011110.1021/acs.jpclett.5c00111","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00111https://doi.org/10.1021/acs.jpclett.5c00111","url":null,"abstract":"Ceramic composites are essential materials for high-performance applications in aerospace, defense, and other industries requiring high-temperature structural components and thermal barrier coatings. However, the understanding of heat transport processes at elevated temperatures, particularly at heterogeneous interfaces, remains in its early stages. In this study, we simulate the thermal transport properties of SiC/Si interfaces at various temperatures and uncover an unexpected anomaly. At high temperatures, the interfacial thermal resistance initially remains stable (consistent with the Acoustic Mismatch Model, AMM) but then decreases anomalously as temperature rises, which finally reaches a plateau as temperature further increases. This behavior results from the interplay between two factors: the gradual melting of Si, which increases the phonon density of states overlap between SiC and Si at the interface, and the gradual reduction in the structure factor of Si due to loss of long-range order. These effects together drive the reduction and subsequent plateau in thermal resistance at the heterogeneous interface in extreme high-temperature conditions. Our findings provide new insights into the complex role of interfacial melting in ultrahigh-temperature heat transfer and offer a theoretical foundation for the design and optimization of ceramic matrix composites for next-generation thermal management solutions in extreme environments.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 12","pages":"3086–3091 3086–3091"},"PeriodicalIF":4.8,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703687","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

Modeling Raman Spectra in Complex Environments: From Solutions to Surface-Enhanced Raman Scattering

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.4c03591

Tommaso Giovannini, Sara Gómez, Chiara Cappelli

引用次数: 0

Strain-Engineered Thermoelectric Performance in Superatomic Semiconductor Re6Se8Cl2: The Role of Four-Phonon Scattering and Coherent Phonons

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c00404

Xiangyu Zeng, Guangming Niu, Xiaowei Wang, Jutao Jiang, Laizhi Sui, Yutong Zhang, Anmin Chen, Mingxing Jin, Kaijun Yuan

{"title":"Strain-Engineered Thermoelectric Performance in Superatomic Semiconductor Re6Se8Cl2: The Role of Four-Phonon Scattering and Coherent Phonons","authors":"Xiangyu Zeng, Guangming Niu, Xiaowei Wang, Jutao Jiang, Laizhi Sui, Yutong Zhang, Anmin Chen, Mingxing Jin, Kaijun Yuan","doi":"10.1021/acs.jpclett.5c00404","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00404","url":null,"abstract":"Strain engineering is an effective strategy to enhance the thermoelectric performance of materials by tuning their phonon and electron transport properties. We investigate the thermoelectric properties of the van der Waals superatomic semiconductor Re6Se8Cl2 under compressive and tensile strain, focusing on its phonon dynamics and thermal transport mechanisms. Through first-principles calculations and self-consistent phonon theory, we reveal the critical role of anharmonic phonon interactions, achieving a remarkably low lattice thermal conductivity of 0.36 W/(m K) at 300 K by incorporating four-phonon scattering and coherent phonon contributions. Compressive strain enhances coherent phonon effects, revealing a complex interplay between diffusive and wave-like thermal transport. For p-type doping, strain-induced changes in carrier effective mass and scattering mechanisms significantly improve carrier mobility and the Seebeck coefficient, achieving a thermoelectric figure of merit (ZT) of 2.12 at 600 K. This study underscores the potential of strain engineering and coherent phonons in designing high-performance thermoelectric materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"206 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653829","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

Generalized Many-Body Perturbation Theory for the Electron Correlation Energy: Multireference Random Phase Approximation via Diagrammatic Resummation

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c00258

Yuqi Wang, Wei-Hai Fang, Zhendong Li

{"title":"Generalized Many-Body Perturbation Theory for the Electron Correlation Energy: Multireference Random Phase Approximation via Diagrammatic Resummation","authors":"Yuqi Wang, Wei-Hai Fang, Zhendong Li","doi":"10.1021/acs.jpclett.5c00258","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00258","url":null,"abstract":"Many-body perturbation theory (MBPT) based on Green’s functions and Feynman diagrams provides a fundamental theoretical framework for various ab initio computational approaches in molecular and materials science, including the random phase approximation (RPA) and GW approximation. Unfortunately, this perturbation expansion often fails in systems with strong multireference characters. Extending diagrammatic MBPT to the multireference case is highly nontrivial and remains largely unexplored, primarily due to the breakdown of Wick’s theorem. In this work, we develop a diagrammatic multireference generalization of MBPT for computing correlation energies of strongly correlated systems, by using the cumulant expansion of many-body Green’s functions in place of Wick’s theorem. This theoretical framework bridges the gap between MBPT in condensed matter physics and multireference perturbation theories (MRPT) in quantum chemistry, which had been almost exclusively formulated within time-independent wave function frameworks prior to this work. Our formulation enables the explicit incorporation of strong correlation effects from the outset as in MRPT, while treating residual weak interactions through a generalized diagrammatic perturbation expansion as in MBPT. As a concrete demonstration, we formulate a multireference (MR) extension of the standard single-reference (SR) RPA by systematically resumming generalized ring diagrams, which naturally leads to a unified set of equations applicable to both SR and MR cases. Benchmark calculations on prototypical molecular systems reveal that MR-RPA successfully resolves the well-known failure of SR-RPA in strongly correlated systems. This theoretical advancement paves the way for advancing ab initio computational methods through diagrammatic resummation techniques in future.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"69 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640887","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

Interplay of Charge Transfer and Local Triplet States in Donor–Acceptor-Based TADF Compounds

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c00241

Tomas Serevičius, Sigitas Tumkevičius, Jelena Dodonova-Vaitku̅nienė, Saulius Juršėnas

引用次数: 0

Strongly Correlated States of Transition Metal Spin Defects: The Case of an Iron Impurity in Aluminum Nitride

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-18 DOI: 10.1021/acs.jpclett.5c0028710.1021/acs.jpclett.5c00287

Leon Otis, Yu Jin, Victor Wen-zhe Yu, Siyuan Chen, Laura Gagliardi* and Giulia Galli*,

引用次数: 0