The Journal of Chemical Physics最新文献

Excited-state properties of functionalized corrole photosensitizers: Insights from ultrafast experiments and quantum mechanical calculations 功能化光敏剂的激发态性质：来自超快实验和量子力学计算的见解

The Journal of Chemical Physics Pub Date : 2025-08-22 DOI: 10.1063/5.0264216

Yubiao Yang, Huahua Huang, Xiaolan Huo, Yi Tang, Wen Han, Jinchang Yin

{"title":"Excited-state properties of functionalized corrole photosensitizers: Insights from ultrafast experiments and quantum mechanical calculations","authors":"Yubiao Yang, Huahua Huang, Xiaolan Huo, Yi Tang, Wen Han, Jinchang Yin","doi":"10.1063/5.0264216","DOIUrl":"https://doi.org/10.1063/5.0264216","url":null,"abstract":"Corrole complex, as a new generation of porphyrin photosensitizer, shows promising applications in photodynamic therapy and optical imaging due to their unique structure and properties. However, lack of comprehensive understanding of the relationship between structure and property limits tailored preparation of demanding corroles. Here, we systematically investigate the excited-state properties of corrole complexes with diverse peripheral substitutions and central atom coordination through time-resolved fluorescence, femtosecond transient absorption spectra, and time-dependent density functional theory calculations. The results indicate that aromatic substituents affect frontier molecular orbitals, prompting intramolecular charge transfer. Coordination with main group P(V) and Ga(III) enhances macrocycle rigidity and symmetry, significantly boosting fluorescence emission rates and absorption efficiency of the Soret band, while improving intersystem crossing probabilities. Transition metal Mn(III) accelerates charge transfer from ligands to metal and shortens internal conversion and intersystem crossing times via d–pπ bonding interaction. This study establishes a foundational understanding for designing high-performance photosensitizers.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermodynamic quantum Fokker–Planck equations and their application to thermostatic Stirling engine 热力学量子福克-普朗克方程及其在恒温斯特林发动机中的应用

The Journal of Chemical Physics Pub Date : 2024-09-19 DOI: 10.1063/5.0225607

Shoki Koyanagi, Yoshitaka Tanimura

{"title":"Thermodynamic quantum Fokker–Planck equations and their application to thermostatic Stirling engine","authors":"Shoki Koyanagi, Yoshitaka Tanimura","doi":"10.1063/5.0225607","DOIUrl":"https://doi.org/10.1063/5.0225607","url":null,"abstract":"We developed a computer code for the thermodynamic quantum Fokker–Planck equations (T-QFPE), derived from a thermodynamic system–bath model. This model consists of an anharmonic subsystem coupled to multiple Ohmic baths at different temperatures, which are connected to or disconnected from the subsystem as a function of time. The code numerically integrates the T-QFPE and their classical expression to simulate isothermal, isentropic, thermostatic, and entropic processes in both quantum and classical cases. The accuracy of the results was verified by comparing the analytical solutions of the Brownian oscillator. In addition, we illustrated a breakdown of the Markovian Lindblad-master equation in the pure quantum regime. As a demonstration, we simulated a thermostatic Stirling engine employed to develop non-equilibrium thermodynamics [S. Koyanagi and Y. Tanimura, J. Chem. Phys. 161, 114113 (2024)] under quasi-static conditions. The quasi-static thermodynamic potentials, described as intensive and extensive variables, were depicted as work diagrams. In the classical case, the work done by the external field is independent of the system–bath coupling strength. In contrast, in the quantum case, the work decreases as the coupling strength increases due to quantum entanglement between the subsystem and bath. The codes were developed for multicore processors using Open Multi-Processing (OpenMP) and for graphics processing units using the Compute Unified Device Architecture. These codes are provided in the supplementary material.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"118 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

GW with hybrid functionals for large molecular systems 大型分子系统的混合函数 GW

The Journal of Chemical Physics Pub Date : 2024-09-19 DOI: 10.1063/5.0219839

Tucker Allen, Minh Nguyen, Daniel Neuhauser

引用次数: 0

Classical and quantum thermodynamics in a non-equilibrium regime: Application to thermostatic Stirling engine 非平衡状态下的经典和量子热力学：热静力斯特林发动机的应用

The Journal of Chemical Physics Pub Date : 2024-09-19 DOI: 10.1063/5.0220685

Shoki Koyanagi, Yoshitaka Tanimura

{"title":"Classical and quantum thermodynamics in a non-equilibrium regime: Application to thermostatic Stirling engine","authors":"Shoki Koyanagi, Yoshitaka Tanimura","doi":"10.1063/5.0220685","DOIUrl":"https://doi.org/10.1063/5.0220685","url":null,"abstract":"We have developed a thermodynamic theory in the non-equilibrium regime, which we describe as a thermodynamic system–bath model [Koyanagi and Tanimura, J. Chem. Phys. 160, 234112 (2024)]. Based on the dimensionless (DL) minimum work principle, non-equilibrium thermodynamic potentials are expressed in terms of non-equilibrium extensive and intensive variables in time derivative form. This is made possible by incorporating the entropy production rate into the definition of non-equilibrium thermodynamic potentials. These potentials can be evaluated from the DL non-equilibrium-to-equilibrium minimum work principle, which is derived from the principle of DL minimum work and is equivalent to the second law of thermodynamics. We thus obtain the non-equilibrium Massieu–Planck potentials as entropic potentials and the non-equilibrium Helmholtz–Gibbs potentials as free energies. Unlike the fluctuation theorem and stochastic thermodynamics theory, this theory does not require the assumption of a factorized initial condition and is valid in the full quantum regime, where the system and bath are quantum mechanically entangled. Our results are numerically verified by simulating a thermostatic Stirling engine consisting of two isothermal processes and two thermostatic processes using the quantum hierarchical Fokker–Planck equations and the classical Kramers equation derived from the thermodynamic system–bath model. We then show that, from weak to strong system–bath interactions, the thermodynamic process can be analyzed using a non-equilibrium work diagram analogous to the equilibrium one for given time-dependent intensive variables. The results can be used to develop efficient heat machines in non-equilibrium regimes.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Time-dependent orbital-optimized coupled-cluster methods families for fermion-mixtures dynamics 费米子混合物动力学的时变轨道优化耦合簇方法家族

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0227236

Haifeng Lang, Takeshi Sato

引用次数: 0

The “simple” photochemistry of thiophene 噻吩的 "简单 "光化学作用

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0226105

Michael A. Parkes, Graham A. Worth

引用次数: 0

Controlling size and distribution of Au nano-particles on C3N4 for high-efficiency photocatalytic hydrogen production 控制 C3N4 上金纳米粒子的尺寸和分布，实现高效光催化制氢

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0226926

Xunan Ran, Zhihua Chen, Hongzhou Ji, Zhaoyu Ma, Yuxi Xie, Wenping Li, Junying Zhang

{"title":"Controlling size and distribution of Au nano-particles on C3N4 for high-efficiency photocatalytic hydrogen production","authors":"Xunan Ran, Zhihua Chen, Hongzhou Ji, Zhaoyu Ma, Yuxi Xie, Wenping Li, Junying Zhang","doi":"10.1063/5.0226926","DOIUrl":"https://doi.org/10.1063/5.0226926","url":null,"abstract":"With advantages such as low cost, high stability, and ease of production, visible light photocatalytic C3N4 with a unique microscopic layered structure holds significant potential for development. However, its hydrogen production efficiency remains low due to the pronounced recombination of photo-generated charge carriers and limited surface reaction sites. Normally, the photocatalytic performance of C3N4 can be enhanced by loading noble metals with surface plasmon resonance. It is worth noting that the size of noble metal nanoparticles has a great influence on photocatalytic performance. In this study, accurate controlling of the size and distribution of Au nanoparticles was achieved on the surface of C3N4 by introducing amino groups to improve photocatalytic performance. Results show that uniformly distributed Au nanoparticles in the range of 2–6 nm can be obtained on C3N4 with a remarkable enhancement of hydrogen production efficiency, which is about 114 times the property of pure C3N4. The small-sized and uniformly distributed Au nanoparticles can provide more reaction sites and increase the separation of photo-generated charge carriers, in turn improving Au/NH3–C3N4 photocatalytic hydrogen release rate to 6.85 mmol g−1 h−1. This work offers a facile way to enhance photocatalytic performance by controlling the size of metal nanoparticles on C3N4 precisely.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kohn–Sham fragment energy decomposition analysis Kohn-Sham 碎片能量分解分析

The Journal of Chemical Physics Pub Date : 2024-09-13 DOI: 10.1063/5.0216596

Tommaso Giovannini

引用次数: 0

Non-equilibrium rate theory for polariton relaxation dynamics 极化子弛豫动力学的非平衡速率理论

The Journal of Chemical Physics Pub Date : 2024-09-13 DOI: 10.1063/5.0231396

Yifan Lai, Wenxiang Ying, Pengfei Huo

引用次数: 0

Designing a hollow MoSe2/CuS nanospheres type-II heterojunction photocatalyst with superior UV–vis-NIR absorption for photocatalytic degradation of organic pollutants 设计具有优异紫外-可见-近红外吸收能力的中空 MoSe2/CuS 纳米球 II 型异质结光催化剂，用于光催化降解有机污染物

The Journal of Chemical Physics Pub Date : 2024-09-13 DOI: 10.1063/5.0209430

Zhilong Zhang, Rong Wu, Jianyong Yue, YaLi Zhu, JiaLei Hui

{"title":"Designing a hollow MoSe2/CuS nanospheres type-II heterojunction photocatalyst with superior UV–vis-NIR absorption for photocatalytic degradation of organic pollutants","authors":"Zhilong Zhang, Rong Wu, Jianyong Yue, YaLi Zhu, JiaLei Hui","doi":"10.1063/5.0209430","DOIUrl":"https://doi.org/10.1063/5.0209430","url":null,"abstract":"In this work, a hollow MoSe2/CuS type-II heterojunction was fabricated using hollow MoSe2 nanospheres as the basis for structural design. UV–Vis–NIR diffuse absorption tests show that MoSe2/CuS has a broad spectral absorption to extend the optical response range from UV–Vis to NIR. The light source utilization rate and interfacial area are increased by the hollow MoSe2/CuS core–shell structure. The broad absorption ability of MoSe2/CuS can facilitate the photocatalysis process. As the electrochemical impedance of MoSe2/CuS is lower than that of the MoSe2, MoSe2/CuS has a good photogenerated carrier separation efficiency. Benefiting from the synergistic facilitation effect of the multi-level 3D hollow nanosphere and the significant space charge region in type-II heterojunction, the RhB degradation efficiency of MoSe2/CuS reached 96.0% in 120.0 min under Xe (350 W) broadband spectrum light irradiation. The photocatalysis mechanism of the hollow MoSe2/CuS core–shell structure was investigated. This work provides an insight into the application of broad spectrum semiconductor heterojunctions to solve environmental problems.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0