The Journal of Chemical Physics最新文献

Substitutional Cu doping at the cation sites in Ba2YNbO6 toward improved visible-light photoactivity—A first-principles HSE06 study 在 Ba2YNbO6 的阳离子位点掺杂铜以提高可见光光活性--第一原理 HSE06 研究

The Journal of Chemical Physics Pub Date : 2024-09-19 DOI: 10.1063/5.0221428

Sankha Ghosh

{"title":"Substitutional Cu doping at the cation sites in Ba2YNbO6 toward improved visible-light photoactivity—A first-principles HSE06 study","authors":"Sankha Ghosh","doi":"10.1063/5.0221428","DOIUrl":"https://doi.org/10.1063/5.0221428","url":null,"abstract":"Artificial photosynthesis holds immense promise for sustainable clean energy harvesting, with recent strides in material engineering with the earth abundant elements enabling efficient utilization of the visible solar spectrum for photoelectrochemical catalytic water splitting. Here, we have investigated the impact of substitutional Cu doping at all three cation sites in Ba2YNbO6 (BYN) using density functional theory calculations at the Heyd-Scuseria-Ernzerhof-06 level. One of the key findings is that the defect formation energy follows the hierarchy Nb &gt; Ba &gt; Y. The presence of an oxygen vacancy (OV) enhances the co-solubility of Cu substitution of Nb, particularly when placed outside the CuO6 unit, while it has a contrary effect for Y substitution. Cu replacement reduces the bandgap as Nb &gt; Y ≫ Ba vis-à-vis pure BYN, while extending it into the visible part of the solar spectrum for Nb and Y replacement cases, albeit with OV causing a slight blue shift to them, without reducing the oxidation state of Cu due to strong charge-delocalization. Cu doping at Y and Nb sites retains the direct band transition character of BYN, a feature removed by OV. While all the bare Cu doped systems exhibit formation of a weak electron polaron, the placement of OV tends to annihilate this except for the system comprising first nearest neighbor placement of an OV relative to the Cu substitution at an Nb site. Notably, Cu doping at the Nb site significantly enhances optical activity, particularly ∼2.0–2.5 eV, resulting in promising candidates for photoelectrochemical catalysts.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260440","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

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

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

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

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

Development of phase-cycling interface-specific two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy 开发特定于相位循环界面的二维电子总和频率发生（2D-ESFG）光谱学

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0227560

Zhi-Chao Huang-Fu, Yuqin Qian, Tong Zhang, Jesse B. Brown, Yi Rao

{"title":"Development of phase-cycling interface-specific two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy","authors":"Zhi-Chao Huang-Fu, Yuqin Qian, Tong Zhang, Jesse B. Brown, Yi Rao","doi":"10.1063/5.0227560","DOIUrl":"https://doi.org/10.1063/5.0227560","url":null,"abstract":"Two-dimensional electronic spectroscopy (2D-ES) has become an important technique for studying energy transfer, electronic coupling, and electronic–vibrational coherence in the past ten years. However, since 2D-ES is not interface specific, the electronic information at surfaces and interfaces could not be demonstrated clearly. Two-dimensional electronic sum-frequency generation (2D-ESFG) is an emerging spectroscopic technique that explores the correlations between different interfacial electronic transitions and is the extension of 2D-ES to surface and interfacial specificity. In this work, we present the detailed development and implementation of phase-cycling 2D-ESFG spectroscopy using an acousto-optic pulse shaper in a pump–probe geometry. With the pulse pair generated by a pulse shaper rather than optical devices based on birefringence or interference, this 2D-ESFG setup enables rapid scanning, phase cycling, and the separation of rephasing and nonrephasing signals. In addition, by collecting data in a rotating frame, we greatly improve experimental efficiency. We demonstrate the method for azo-derivative molecules at the air/water interface. This method could be readily extended to different interfaces and surfaces. The unique phase-cycling 2D-ESFG technique enables one to quantify the energy transfer, charge transfer, electronic coupling, and many other electronic properties and dynamics at surfaces and interfaces with precision and relative ease of use. Our goal in this article is to present the fine details of the fourth-order nonlinear optical technique in a manner that is comprehensive, succinct, and approachable such that other researchers can implement, improve, and adapt it to probe unique and innovative problems to advance the field.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"207 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260506","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

Optimization of damping function parameters for -D3 and -D4 dispersion models for Hartree–Fock based symmetry-adapted perturbation theory 基于哈特里-福克对称适配扰动理论的 -D3 和 -D4 弥散模型的阻尼函数参数优化

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0219185

Austin M. Wallace, C. David Sherrill

{"title":"Optimization of damping function parameters for -D3 and -D4 dispersion models for Hartree–Fock based symmetry-adapted perturbation theory","authors":"Austin M. Wallace, C. David Sherrill","doi":"10.1063/5.0219185","DOIUrl":"https://doi.org/10.1063/5.0219185","url":null,"abstract":"Symmetry-adapted perturbation theory (SAPT) directly computes intermolecular interaction energy in terms of electrostatics, exchange-repulsion, induction/polarization, and London dispersion components. In SAPT based on Hartree–Fock (“SAPT0”) or based on density functional theory, the most time-consuming step is the computation of the dispersion terms. Previous work has explored the replacement of these expensive dispersion terms with simple damped asymptotic models. We recently examined [Schriber et al. J. Chem. Phys. 154, 234107 (2021)] the accuracy of SAPT0 when replacing its dispersion term with Grimme’s popular -D3 correction, reducing the computational cost scaling from O(N5) to O(N3). That work optimized damping function parameters for SAPT0-D3/jun-cc-pVDZ using estimates of the coupled-cluster complete basis set limit [CCSD(T)/CBS] on a 8299 dimer dataset. Here, we explore the accuracy of SAPT0-D3 with additional basis sets, along with an analogous model using -D4. Damping parameters are rather insensitive to basis sets, and the resulting SAPT0-D models are more accurate on average for total interaction energies than SAPT0. Our results are surprising in several respects: (1) improvement of -D4 over -D3 is negligible for these systems, even charged systems where -D4 should, in principle, be more accurate; (2) addition of Axilrod–Teller–Muto terms for three-body dispersion does not improve error statistics for this test set; and (3) SAPT0-D is even more accurate on average for total interaction energies than the much more computationally costly density functional theory based SAPT [SAPT(DFT)] in an aug-cc-pVDZ basis. However, SAPT0 and SAPT0-D3/D4 interaction energies benefit from significant error cancellation between exchange and dispersion terms.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260503","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

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

Cluster intercalation of aluminum tetrachloride in AlN cathode: Exploration and analysis of aluminum ion batteries 氮化铝阴极中的四氯化铝簇插层：铝离子电池的探索与分析

The Journal of Chemical Physics Pub Date : 2024-09-18 DOI: 10.1063/5.0219080

Shanshan He, Leilei Li, Yijin Wu, Shan He, Donghui Guo

{"title":"Cluster intercalation of aluminum tetrachloride in AlN cathode: Exploration and analysis of aluminum ion batteries","authors":"Shanshan He, Leilei Li, Yijin Wu, Shan He, Donghui Guo","doi":"10.1063/5.0219080","DOIUrl":"https://doi.org/10.1063/5.0219080","url":null,"abstract":"When chloroaluminate (AlCl4−) serves as the electrolyte, aluminum nitride (AlN) has shown promise as a cathode material in aluminum ion batteries. However, there is currently a lack of research on the mechanisms of charge transfer and cluster intercalation between AlCl4 and AlN cathode materials. Herein, first-principles calculations are employed to investigate the intercalation mechanism of AlCl4 within the AlN cathode. By calculating the formation energies of stage-1–5 AlN–AlCl4 intercalation compounds with the insertion of individual AlCl4 cluster, we found that the structure of the stage-4 intercalation compounds exhibits the highest stability, suggesting that when the clusters begin to intercalate, it is important to start with the formation of the stage-4 intercalation compounds. In the subsequent phases of the charging process (stages 1 and 2), the stabilized structure with four inserted clusters demonstrates two characteristics: the coexistence of standing and lying clusters and the insertion of two standing clusters in an upside-down doubly stacked configuration, which further improve the spatial utilization while maintaining the structural stability. In addition, we infer that a phenomenon of coexisting intercalation compounds with mixed stages will occur in the course of the charging and discharging processes. More importantly, the diffusion barrier of AlCl4 in AlN–AlCl4 intercalation compounds decreases with the reduction of stage number, ensuring the rate performance of batteries. Therefore, we expect that our work will contribute to comprehend the intercalation mechanism of AlCl4 into the AlN cathode materials of aluminum ion batteries, providing guidance for related experimental work.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"86 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260505","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