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 > Ba > 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 > 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.
人工光合作用为可持续的清洁能源采集带来了巨大的前景，最近在材料工程中使用地球上丰富的元素取得了长足的进步，从而能够有效地利用可见太阳光谱进行光电化学催化水分离。在此，我们利用海德-斯库塞里亚-恩泽霍夫-06 水平的密度泛函理论计算，研究了在 Ba2YNbO6（BYN）的所有三个阳离子位点掺杂铜的影响。主要发现之一是缺陷形成能遵循 Nb > Ba > Y 的层次结构。氧空位（OV）的存在增强了 Cu 取代 Nb 的共溶性，尤其是当其位于 CuO6 单元之外时，而对 Y 取代则有相反的影响。与纯铍青铜相比，当 Nb > Y ≫ Ba 时，铜置换降低了带隙，而在 Nb 和 Y 置换的情况下，带隙扩展到了太阳光谱的可见光部分，尽管 OV 会导致它们发生轻微的蓝移，但不会因为强烈的电荷迁移而降低铜的氧化态。在 Y 和 Nb 位点掺入的铜保留了 BYN 的直接带过渡特性，而 OV 则消除了这一特性。虽然所有裸掺杂铜的体系都会形成微弱的电子极子，但除了在铌位点掺杂铜取代物的第一近邻位点掺杂 OV 的体系外，其他掺杂 OV 的体系都倾向于湮灭电子极子。值得注意的是，在铌位点掺入铜可显著提高光学活性，尤其是在 2.0-2.5 eV 之间，从而有望成为光电化学催化剂的候选物质。
{"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 > Ba > 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 > 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}
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.
我们开发了一种非平衡态热力学理论，并将其描述为热力学系统-浴模型[Koyanagi and Tanimura, J. Chem. Phys. 160, 234112 (2024)]。根据无量纲（DL）最小功原理，非平衡热力学势可以用时间导数形式的非平衡广泛变量和密集变量来表示。通过将熵产生率纳入非平衡热力学势的定义，这一点成为可能。这些势能可根据 DL 非平衡到平衡最小功原理进行评估，该原理源于 DL 最小功原理，等同于热力学第二定律。因此，我们可以得到作为熵势的非平衡马修-普朗克势和作为自由能的非平衡亥姆霍兹-吉布斯势。与波动定理和随机热力学理论不同的是，该理论不需要假设因子化初始条件，并且在系统和浴槽量子力学纠缠的全量子体系中有效。我们利用量子分层福克-普朗克方程和从热力学系统-浴模型中推导出的经典克拉默方程，模拟了一台由两个等温过程和两个恒温过程组成的恒温斯特林发动机，从数值上验证了我们的结果。然后我们证明，从弱系统-水浴相互作用到强系统-水浴相互作用，热力学过程都可以使用非平衡功图进行分析，类似于给定时间相关密集变量的平衡功图。这些结果可用于开发非平衡状态下的高效热机。
{"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}
A low-cost approach for stochastically sampling static exchange during time-dependent Hartree–Fock-type propagation is presented. This enables the use of an excellent hybrid density functional theory (DFT) starting point for stochastic GW quasiparticle energy calculations. Generalized Kohn–Sham molecular orbitals and energies, rather than those of a local-DFT calculation, are used for building the Green function and effective Coulomb interaction. The use of an optimally tuned hybrid diminishes the starting point dependency in one-shot stochastic GW, effectively avoiding the need for self-consistent GW iterations.
{"title":"GW with hybrid functionals for large molecular systems","authors":"Tucker Allen, Minh Nguyen, Daniel Neuhauser","doi":"10.1063/5.0219839","DOIUrl":"https://doi.org/10.1063/5.0219839","url":null,"abstract":"A low-cost approach for stochastically sampling static exchange during time-dependent Hartree–Fock-type propagation is presented. This enables the use of an excellent hybrid density functional theory (DFT) starting point for stochastic GW quasiparticle energy calculations. Generalized Kohn–Sham molecular orbitals and energies, rather than those of a local-DFT calculation, are used for building the Green function and effective Coulomb interaction. The use of an optimally tuned hybrid diminishes the starting point dependency in one-shot stochastic GW, effectively avoiding the need for self-consistent GW iterations.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"37 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260441","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}
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.
我们开发了热力学量子福克-普朗克方程（T-QFPE）的计算机代码，该代码源自热力学系统-浴模型。该模型由一个非谐波子系统和多个不同温度的欧姆浴耦合组成，欧姆浴随时间的变化与子系统连接或断开。该代码对 T-QFPE 及其经典表达式进行数值积分，以模拟量子和经典情况下的等温、等熵、恒温和熵过程。通过比较布朗振荡器的分析解，验证了结果的准确性。此外，我们还说明了马尔可夫林德布拉德-马斯特方程在纯量子体系中的分解。作为演示，我们模拟了准静态条件下的恒温斯特林发动机，该发动机用于发展非平衡热力学 [S. Koyanagi and Y. Tanimura, J. Chem. Phys. 161, 114113 (2024)]。准静态热力学势被描述为密集变量和广义变量，并被描绘成功图。在经典情况下，外部场做的功与系统-浴耦合强度无关。相反，在量子情况下，由于子系统与浴槽之间的量子纠缠，功随耦合强度的增加而减小。这些代码是为使用开放多处理（OpenMP）的多核处理器和使用计算统一设备架构的图形处理单元开发的。这些代码在补充材料中提供。
{"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}
Five time-dependent orbital optimized coupled-cluster methods, of which four can converge to the time-dependent complete active space self-consistent-field method, are presented for fermion-mixtures with arbitrary fermion kinds and numbers. Truncation schemes maintaining the intragroup orbital rotation invariance, as well as equations of motion of coupled-cluster (CC) amplitudes and orbitals, are derived. Present methods are compact CC-parameterization alternatives to the time-dependent multiconfiguration self-consistent-field method for systems consisting of arbitrarily different kinds and numbers of interacting fermions. Theoretical analysis of applications of present methods to various chemical systems is reported.
针对具有任意费米子种类和数量的费米子混合物，提出了五种随时间变化的轨道优化耦合簇方法，其中四种可收敛于随时间变化的完整活动空间自洽场方法。推导了保持组内轨道旋转不变性的截断方案，以及耦合簇（CC）振幅和轨道的运动方程。对于由任意不同种类和数量的相互作用费米子组成的系统，目前的方法是时间相关多配置自洽场方法的紧凑型 CC 参数化替代方法。报告还对本方法在各种化学体系中的应用进行了理论分析。
{"title":"Time-dependent orbital-optimized coupled-cluster methods families for fermion-mixtures dynamics","authors":"Haifeng Lang, Takeshi Sato","doi":"10.1063/5.0227236","DOIUrl":"https://doi.org/10.1063/5.0227236","url":null,"abstract":"Five time-dependent orbital optimized coupled-cluster methods, of which four can converge to the time-dependent complete active space self-consistent-field method, are presented for fermion-mixtures with arbitrary fermion kinds and numbers. Truncation schemes maintaining the intragroup orbital rotation invariance, as well as equations of motion of coupled-cluster (CC) amplitudes and orbitals, are derived. Present methods are compact CC-parameterization alternatives to the time-dependent multiconfiguration self-consistent-field method for systems consisting of arbitrarily different kinds and numbers of interacting fermions. Theoretical analysis of applications of present methods to various chemical systems is reported.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260502","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}
Zhi-Chao Huang-Fu, Yuqin Qian, Tong Zhang, Jesse B. Brown, Yi Rao
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.
{"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}
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.
{"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}
The static gas-phase (“simple”) ultraviolet absorption spectrum of thiophene is investigated using a combination of a vibronic coupling model Hamiltonian with multi-configuration time-dependent Hartree quantum dynamics simulations. The model includes five states and all 21 vibrations, with potential surfaces calculated at the complete active space with second-order perturbation level of theory. The model includes terms up to eighth-order to describe the diabatic potentials. The resulting spectrum is in excellent agreement with the experimentally measured spectrum of Holland et al. [Phys. Chem. Chem. Phys. 16, 21629 (2014)]. The, until now not understood, spectral features are assigned, with a combination of strongly coupled vibrations and vibronic coupling between the states giving rise to a progression of triplets on the rising edge of the broad spectrum. The analysis of the underlying dynamics indicates that population transfer between all states takes place on a sub-100 fs timescale, with ring-opening occurring at longer times. The model thus provides a starting point for further investigations into the complicated photo-excited dynamics of this key hetero-aromatic molecule.
采用振子耦合模型哈密顿与多配置时变哈特里量子动力学模拟相结合的方法，研究了噻吩的静态气相（"简单"）紫外吸收光谱。该模型包括五种状态和所有 21 个振动，其势能面是在完整的活性空间以二阶扰动理论水平计算得出的。该模型包括高达八阶的项来描述二态势。所得到的光谱与 Holland 等人的实验测量光谱非常吻合[Phys.迄今为止还不为人所知的光谱特征是由强耦合振动和态之间的振子耦合共同作用而产生的，在宽光谱的上升沿出现了三连串。对基本动力学的分析表明，所有状态之间的种群转移都发生在 100 fs 以下的时间尺度上，而开环则发生在更长的时间内。因此，该模型为进一步研究这种关键杂芳香族分子的复杂光激发动力学提供了一个起点。
{"title":"The “simple” photochemistry of thiophene","authors":"Michael A. Parkes, Graham A. Worth","doi":"10.1063/5.0226105","DOIUrl":"https://doi.org/10.1063/5.0226105","url":null,"abstract":"The static gas-phase (“simple”) ultraviolet absorption spectrum of thiophene is investigated using a combination of a vibronic coupling model Hamiltonian with multi-configuration time-dependent Hartree quantum dynamics simulations. The model includes five states and all 21 vibrations, with potential surfaces calculated at the complete active space with second-order perturbation level of theory. The model includes terms up to eighth-order to describe the diabatic potentials. The resulting spectrum is in excellent agreement with the experimentally measured spectrum of Holland et al. [Phys. Chem. Chem. Phys. 16, 21629 (2014)]. The, until now not understood, spectral features are assigned, with a combination of strongly coupled vibrations and vibronic coupling between the states giving rise to a progression of triplets on the rising edge of the broad spectrum. The analysis of the underlying dynamics indicates that population transfer between all states takes place on a sub-100 fs timescale, with ring-opening occurring at longer times. The model thus provides a starting point for further investigations into the complicated photo-excited dynamics of this key hetero-aromatic molecule.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260445","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}
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.
{"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}
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.
{"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}
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