Journal of Chemical Physics最新文献_第4页

Automated potential energy surface development and quasi-classical dynamics for the F- + SiH3I system. F- + SiH3I 系统的自动势能面开发和准经典动力学。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0238366

Balázs J Molnár, Attila Á Dékány, Gábor Czakó

{"title":"Automated potential energy surface development and quasi-classical dynamics for the F- + SiH3I system.","authors":"Balázs J Molnár, Attila Á Dékány, Gábor Czakó","doi":"10.1063/5.0238366","DOIUrl":"10.1063/5.0238366","url":null,"abstract":"We report a potential energy surface (PES) development for the F- + SiH3I system to study its gas-phase reactions through quasi-classical dynamics simulations. The PES is represented by a full-dimensional permutationally invariant polynomial fitted to composite coupled cluster energy points obtained at the ManyHF-[CCSD-F12b + BCCD(T) - BCCD]/aug-cc-pVTZ(-PP) level of theory. The development was automated by Robosurfer, which samples the configurational space, manages ab initio calculations, and iteratively extends the fitting set. When selecting the ab initio method, we address two types of electronic structure calculation issues: first, the gold standard CCSD(T)-F12b is prone to occasional breakdown due to the perturbative (T) contribution, whereas CCSD-F12b + BCCD(T) - BCCD, with the Brueckner (T) term, is more robust; second, the underlying Hartree-Fock calculation may not always converge to the global minimum, resulting in highly erroneous energies. To mitigate this, we employed ManyHF, configuring the Hartree-Fock calculations with multiple initial guess orbitals and selecting the solution with the lowest energy. According to the simulations, the title system exhibits exceptionally high and diverse reactivity. We observe two dominant product formations: SN2 and proton abstraction. Moreover, SiH2F- + HI, SiHFI- + H2, SiH2FI + H-, SiH2 + FHI-, SiH2 + HF + I-, and SiHF + H2 + I- formations are found at lower probabilities. We differentiated inversion and retention for SN2, both being significant throughout the entire collision energy range. Opacity- and excitation functions are reported, and the details of the atomistic dynamics are visually examined via trajectory animations.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142668167","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

Lagrangian formulation of nuclear-electronic orbital Ehrenfest dynamics with real-time TDDFT for extended periodic systems. 针对扩展周期系统的核电子轨道艾伦费斯特动力学拉格朗日公式与实时 TDDFT。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0230570

Jianhang Xu, Ruiyi Zhou, Tao E Li, Sharon Hammes-Schiffer, Yosuke Kanai

引用次数: 0

Morphology- and crystal packing-dependent singlet fission and photodegradation in functionalized tetracene crystals and films. 功能化梭形四烯晶体和薄膜中与形态和晶体堆积有关的单线裂变和光降解。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0234494

Winston T Goldthwaite, Evan Lambertson, Madalyn Gragg, Dean Windemuller, John E Anthony, Tim J Zuehlsdorff, Oksana Ostroverkhova

{"title":"Morphology- and crystal packing-dependent singlet fission and photodegradation in functionalized tetracene crystals and films.","authors":"Winston T Goldthwaite, Evan Lambertson, Madalyn Gragg, Dean Windemuller, John E Anthony, Tim J Zuehlsdorff, Oksana Ostroverkhova","doi":"10.1063/5.0234494","DOIUrl":"https://doi.org/10.1063/5.0234494","url":null,"abstract":"Singlet fission (SF) is a charge carrier multiplication process that has potential for improving the performance of (opto)electronic devices from the conversion of one singlet exciton S1 into two triplet excitons T1 via a spin-entangled triplet pair state 1(TT). This process depends highly on molecular packing and morphology, both for the generation and dissociation of 1(TT) states. Many benchmark SF materials, such as acenes, are also prone to photodegradation reactions, such as endoperoxide (EPO) formation and photodimerization, which inhibit realization of SF devices. In this paper, we compare functionalized tetracenes R-Tc with two packing motifs: \"slip-stack\" packing in R = TES, TMS, and tBu and \"gamma\" packing in R = TBDMS to determine the effects of morphology on SF as well as on photodegradation using a combination of temperature and magnetic field dependent spectroscopy, kinetic modeling, and time-dependent density functional theory. We find that both \"slip-stack\" and \"gamma\" packing support SF with high T1 yield at room temperature (up to 191% and 181%, respectively), but \"slip-stack\" is considerably more advantageous at low temperatures (<150 K). In addition, each packing structure has a distinct emissive relaxation pathway competitive to SF, while the states involved in the SF itself are dark. The \"gamma\" packing has superior photostability, both in regards to EPO formation and photodimerization. The results indicate that the trade-off between SF efficiency and photostability can be overcome with material design, emphasize the importance of considering both photophysical and photochemical properties, and inform efforts to develop optimal SF materials for (opto)electronic applications.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142681940","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

Enhanced energy storage performance in polyetherimide composites via oriented one-dimensional BZCT@BT core-shell filler. 通过取向一维 BZCT@BT 核壳填料提高聚醚酰亚胺复合材料的储能性能。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0236833

Yu Feng, Jun Sun, Zhonghua Zhang, Puzhen Wang, Wenchao Zhang, Dong Yue, Qingguo Chen

{"title":"Enhanced energy storage performance in polyetherimide composites via oriented one-dimensional BZCT@BT core-shell filler.","authors":"Yu Feng, Jun Sun, Zhonghua Zhang, Puzhen Wang, Wenchao Zhang, Dong Yue, Qingguo Chen","doi":"10.1063/5.0236833","DOIUrl":"10.1063/5.0236833","url":null,"abstract":"The development of dielectric capacitors toward high voltage and high power density requires materials with excellent insulation and energy storage performances. In this work, a polymer dielectric with polyetherimide (PEI) as the matrix and calcium barium zirconate titanate (BZCT) coated by barium titanate fiber (BT) as the filler (BZCT@BT) was constructed. The (0.5%-10% BZCT@BT/PEI) polymer dielectric has an excellent discharge energy density (Ue) of 6.66 J/cm3 and maintains an advanced charge/discharge efficiency (η) of 93.29% when the BT content was 0.5% and the BZCT particle content was 10%. The addition of BZCT endows the polymer dielectric with a higher relative dielectric constant (εr), while BT, maintaining a lower εr than BZCT, could reduce the electric field (E) distortion caused by the dielectric mismatch between PEI and BZCT. Oriented fiber fillers increase the breakdown strength of the polymer dielectric, ultimately increasing the performance of energy storage. A new strategy for the design of energy storage polymer dielectrics was provided by this work.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142668168","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

Machine-learning surrogate models for particle insertions and element substitutions. 粒子插入和元素替换的机器学习代用模型。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0240275

Ryosuke Jinnouchi

{"title":"Machine-learning surrogate models for particle insertions and element substitutions.","authors":"Ryosuke Jinnouchi","doi":"10.1063/5.0240275","DOIUrl":"10.1063/5.0240275","url":null,"abstract":"Two machine-learning-aided thermodynamic integration schemes to compute the chemical potentials of atoms and molecules have been developed and compared. One is the particle insertion method, and the other combines particle insertion with element substitution. In the former method, the species is gradually inserted into the liquid and its chemical potential is computed. In the latter method, after the particle insertion, the inserted species is substituted with another species, and the chemical potential of this new species is computed. In both methods, the thermodynamic integrations are conducted using machine-learned potentials trained on first-principles datasets. The errors of the machine-learned surrogate models are further corrected by performing thermodynamic integrations from the machine-learned potentials to the first-principles potentials, accurately providing the first-principles chemical potentials. These two methods are applied to compute the real potentials of proton, alkali metal cations, and halide anions in water. The applications indicate that these two entirely different thermodynamic pathways yield identical real potentials within statistical error bars, demonstrating that both methods provide reproducible real potentials. The computed real potentials and solvation structures are also in good agreement with past experiments and simulations. These results indicate that machine-learning surrogate models enabling particle insertion and element substitution provide a precise method for determining the chemical potentials of atoms and molecules.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142667526","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

New insights into the dissolution mechanisms of iron oxides and combusted iron particles in oxalic acid. 草酸中铁氧化物和燃烧铁颗粒溶解机制的新见解。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0229410

M Lausch, A Zimina, J Bao, R Pashminehazar, B J M Etzold, U I Kramm, J-D Grunwaldt, J Hussong

{"title":"New insights into the dissolution mechanisms of iron oxides and combusted iron particles in oxalic acid.","authors":"M Lausch, A Zimina, J Bao, R Pashminehazar, B J M Etzold, U I Kramm, J-D Grunwaldt, J Hussong","doi":"10.1063/5.0229410","DOIUrl":"10.1063/5.0229410","url":null,"abstract":"The influence of oxidation state and crystalline structure on the dissolution mechanisms of both pure iron oxides and combusted iron particles in aqueous oxalic acid (0.5 mol/l) at 60 °C was systematically investigated. Dissolution experiments were carried out in a temperature-controlled, continuous-flow capillary reactor, allowing for the removal of reaction products and thereby suppressing the autocatalytic reaction mechanism. The non-reductive dissolution of α-Fe2O3 was observed through in situ x-ray absorption measurements. In contrast, the dissolution of spinel-type oxides such as γ-Fe2O3 and Fe3O4 proceeded reductively, indicated by gradual changes in characteristic spectral features. Given that γ-Fe2O3 and Fe3O4 share a similar crystal structure but differ in the nominal oxidation state, this implies that the phase composition is decisive for the reductive dissolution. For mixed-phase particles consisting of spinel and rhombohedral phases (maghemite and hematite), the preferential dissolution of the spinel phase was observed. Despite the similar bulk composition of spinel and rhombohedral phases in the combusted iron particles (as confirmed by Mössbauer spectroscopy and x-ray diffraction analysis), dissolution predominantly follows a non-reductive pathway, with no preferential dissolution of the γ-phase. This unique dissolution behavior of combusted iron particles arises from their layered microstructure.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142667532","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

Meijer-G and other resummation strategies for the Møller-Plesset perturbation series. 莫勒-普莱塞特扰动序列的 Meijer-G 和其他求和策略。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0238490

Yilin Zhao, Wenbiao Zhang, Chunying Rong, Paul W Ayers

引用次数: 0

Investigation and insights on the on-demand generation of monodispersed emulsion droplets from a floating capillary-based open microfluidic device. 基于浮动毛细管的开放式微流体装置按需生成单分散乳液液滴的研究与见解。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0234937

Yueming Deng, Shuting Xie, Zhengguang Li, Ruizhi Yang, Zhenping Liu, Jiyuan Yao, Haopeng Zhang, Mingliang Jin, Lingling Shui

{"title":"Investigation and insights on the on-demand generation of monodispersed emulsion droplets from a floating capillary-based open microfluidic device.","authors":"Yueming Deng, Shuting Xie, Zhengguang Li, Ruizhi Yang, Zhenping Liu, Jiyuan Yao, Haopeng Zhang, Mingliang Jin, Lingling Shui","doi":"10.1063/5.0234937","DOIUrl":"10.1063/5.0234937","url":null,"abstract":"Simple and stable generation of monodispersed droplets with volume from picolitre to nanoliter is one of the key factors in high-throughput quantitative microreactors for chemical and biomedical applications. In this work, an efficient method that could realize simple manipulating microflow with a broad operation window for preparing monodispersed droplets with controllable diameter is developed. The microfluidic device is constructed by inserting a capillary with an oblique angle (α) into the continuous phase, named a floating capillary-based open microfluidic device (FCOMD). The transition of droplet-generating mode between dripping and jetting can be achieved by changing capillary number and α. A computational model based on the volume-of-fluid/continuum-surface-force method to explain the controllability of α on the droplet formation regime and droplet breakage, verifying the synergistic effect of ΔP and Fb, facilitates the droplet pinching. A descending order of Pn of capillary with different α is that 45° > 30° > 15° > 60° > 75°, leading to the same order of generated droplet's D. When compared with the traditional capillary co-flow device, the generating throughput of the integrated FCOMD obtained by integrating different numbers of capillaries is at least ten times. Moreover, water in oil, oil in water double-emulsion, colloidal dispersed droplets, and liquid crystal droplets with diameters ranging from 25 to 800 μm are prepared on-demand by the FCOMD, indicating the universality of the microfluidic device. Thus, the FCOMD shows the features of simplicity, practicability, and flexibility, offering valuable guidance for generating controllable droplets with wide size change and showing a great potential application in material science, foods, pharmaceuticals, and cosmetics.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666458","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

Photoelectron spectroscopy and theoretical study of Cu(CO)2. Cu(CO)2 的光电子能谱和理论研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0238481

Zhen Li, Wenli Liu, Gaoming Hu, Boxing Zhu, Qiang Zhang, Yang Chen, Dongfeng Zhao

引用次数: 0

An explicitly correlated potential energy surface for N2-OCS complex: Out-of-plane motion and tunneling dynamics. N2-OCS 复合物的显式相关势能面：平面外运动和隧道动力学

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2024-11-21 DOI: 10.1063/5.0238925

Rui Zheng, Tong Cheng, Tongyu Liu, Yanshan Tian

{"title":"An explicitly correlated potential energy surface for N2-OCS complex: Out-of-plane motion and tunneling dynamics.","authors":"Rui Zheng, Tong Cheng, Tongyu Liu, Yanshan Tian","doi":"10.1063/5.0238925","DOIUrl":"10.1063/5.0238925","url":null,"abstract":"A four-dimensional potential energy surface (4D-PES) has been constructed for the N2-OCS complex. The PES is achieved by applying the explicitly correlated coupled cluster method, which incorporates single, double, and perturbative triple excitations [CCSD(T)-F12a], along with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. The rovibrational levels are precisely determined and assigned through bound state calculations and wavefunction analysis. The calculated transition frequencies reproduce the experimental observations accurately, achieving an RMSE of 0.0005 cm-1 for the 23 rotational transitions (J ≤ 6, Ka ≤ 2). The R-φ contour plot of the wave function clearly demonstrates the unambiguous delocalization of the dihedral angle, and the averaged geometry of the ground vibrational state is determined to be non-planar with φ = 90°. To obtain a quantitative analysis of this phenomenon, we expanded the 3H-solution model [Guo et al., J. Quant. Spectrosc. Radiat. Transfer 309 (2023) 108711] from a three-dimensional system (Ar-AgF) to a nine-dimensional system (N2-OCS). Based on this model, the tunneling splitting was calculated to be 0.0822 cm-1, which excellently matches the experimental result of 0.0817 cm-1. The excellent agreement between the theoretical and experimental results suggests that the wavefunction delocalization and out-of-plane motion can be attributed to the tunneling effects in the ground vibrational state.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"161 19","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142668166","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