The Journal of Physical Chemistry C最新文献

{"title":"Short Autobiography of Jens K. Nørskov","authors":"Jens K. Nørskov","doi":"10.1021/acs.jpcc.4c08365","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08365","url":null,"abstract":"Published as part of <i>The Journal of Physical Chemistry C</i> special issue “Jens K. Nørskov Festschrift”. I received a PhD in physics from Århus University, Denmark, under the inspiring supervision of Bengt Lundqvist. After postdoc experiences at Århus University, IBM Yorktown Heights Research Laboratories, and the Nordic Institute for Theoretical Physics in Copenhagen, I found it hard to find a faculty position in Denmark in the early 1980s. There simply were no openings. Fortunately, I was offered a position at the Haldor Topsøe Research Laboratories─strongly supported by Haldor Topsøe, Henrik Topsøe, and Bjerne Clausen. The involvement with the Topsøe company, one of the world’s largest suppliers of catalysts and technology for the chemical and energy industry, influenced my career in many ways. Most importantly, it became clear to me that a theory of heterogeneous catalysis was essential to further advance this important area of science and technology. I kept that focus when starting an academic career, and kept the association with the Topsøe company, now serving on its Board of Directors. In the late 80s the Danish government started to realize that they were about to lose a whole generation of scientists and instituted some special professorships with applicants competing in all fields and at all universities in the country. That got me started at the Technical University of Denmark building up a research group with the funding that came with the professorship. The focus was on understanding surface reactivity as well as impurities in bulk metals. The impurity work started an extremely fruitful collaboration with Flemming Besenbacher at Århus University that continued for the next decades. With Besenbacher, I founded the Center for Atomic- scale Materials Physics with large-scale funding from the first round of grants from the Danish National Research Foundation. Here my group established the beginning of an understanding of the surface chemical bond. It started with simple models like the effective medium theory. Later, as more accurate density functional calculations became possible, it formed the foundation of the d-band model, or Hammer–Nørskov model, of chemisorption. The model allowed an understanding of trends in bond energies of adsorbates on transition metal surfaces including variations from metal to metal, the effect of alloying, the effect of structure and defects, and the effect of strain. The interplay with the experimental groups of Flemming Besenbacher, Ib Chorkendorff and Anders Nilsson became extremely important in supporting the theory efforts. Combining DFT calculations of trends in adsorption energies and transition state energies of elemental surface processes with microkinetic modeling opened the possibility of calculating trends in full catalytic rates, for the first time. This also opened the possibility of making predictions for new catalysts, several of which were synthesized and tested in the groups of Claus ","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"75 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vibration Analysis of Hexagonal Boron Nitride under Electric Field via Semiempirical Quantum Mechanical Method","authors":"Hongqiang Pang, Zhuoqun Zheng, Eric Li, Lifeng Wang","doi":"10.1021/acs.jpcc.4c06873","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06873","url":null,"abstract":"The vibrational behavior of micronano structures is crucial for advancing micronano electromechanical systems (MEMS)-like resonators, oscillators, and sensors. Electric fields significantly influence these devices, but classical molecular dynamics (CMD) lacks a mechanism to account for the effects on electrons and first-principles simulations are constrained by their limited scale. In this study, we employ an extended tight-binding (xTB) semiempirical quantum mechanical method to model the impact of electric fields on a relatively large number of atoms. We specifically investigate the vibration of a 2D hexagonal boron nitride (h-BN) under an electric field. The piezoelectric constants of h-BN are calculated using xTB and compared with density functional theory results. Additionally, we compare the electric field forces between atoms derived from semiempirical quantum mechanical molecular dynamics (SQMD) and CMD simulations. The analysis focuses on the effect of the electric field on natural frequencies. Our findings reveal that CMD considers only the effect of electric field force. However, the electric field force alone cannot fully replicate the effects of an electric field on h-BN, as the field also influences the bond properties in SQMD. Notably, the change of initial strain does not affect the trend of frequency change under an electric field. This investigation into h-BN vibrations under electric fields holds significant importance for the development of MEMS.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nonlocal Effects in Plasmons of Grooved Gold Cylindrical Structures Based on Modified Hydrodynamic Theory","authors":"Xiuwen Xi, Zheng Wang, Heng Zhang, Jianguo Wan, Chuanfu Huang","doi":"10.1021/acs.jpcc.4c07962","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07962","url":null,"abstract":"This work explores the nonlocal behavior of the optical response of infinitely long gold (Au) cylindrical nanostructures (ILANs) with controllable grooves. By varying three parameters, such as the number of grooves, the groove width, and the material of the connector, the systematic calculations of the plasmon resonance peaks of ILANs are performed under classical local theory and modified hydrodynamic (nonlocal) theory. We find that the properties of metallic nanostructures calculated using local theory are not significantly dependent on changes in their size, shape, or environment. However, under nonlocal theory, we observe that the optical properties of ILANs is highly reliant on these three variables. Compare to the classical local theory, we successfully apply the more accurate modified hydrodynamic theory to complex nanometallic structures, which lays a foundation for the theory and design of optical devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"118 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning Committee Neural Network Potential Energy Surfaces for Two-Dimensional Metal–Organic Frameworks","authors":"Yuliang Shi, Farnaz A. Shakib","doi":"10.1021/acs.jpcc.4c07386","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07386","url":null,"abstract":"Two-dimensional (2D) layered metal–organic frameworks (MOFs) are gaining attention due to their unique structural and electronic properties with promising applications in compact electronic device fabrication. Long-time and large-scale molecular dynamics simulations of these materials can enhance and expedite the mapping out of their structure–property–function relationships for these applications. To make such simulations more feasible, herein, we construct a high-dimensional committee neural network potential (CNNP) for archetypal 2D MOFs Ni₃(HIB)₂ and Ni₃(HITP)₂ where HIB = hexaiminobenzene and HITP = hexaiminotriphenylene. We harness the power of active learning and committee neural networks to obtain a CNNP model by using only hundreds of snapshots from ab initio molecular dynamics (AIMD) trajectories. The developed CNNP model allows for simulations of thousands of atoms over extended time scales, which is typically unfeasible with AIMD simulations while maintaining the accuracy of the reference data. Our stable MD simulations based on the developed CNNP model reveal the flexible nature of the studied 2D MOFs at room temperature, including puckered layers, as opposed to the planar ones from 0 K electronic structure calculations. Furthermore, our model demonstrates transferability between bulk and monolayers, as well as different organic linkers. As the first model of its kind, we show that the high-dimensional CNNP models could be a reliable and effective approach for future studies on 2D MOFs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"37 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Laser-Induced Emission Spectra of La0.95Nd0.05MnO3 Nanocrystals","authors":"João M. Gonçalves, Mariusz Stefanski, Robert Tomala, Agata Musialek, Bartłomiej Cichy, Marco Bettinelli, Wieslaw Strek","doi":"10.1021/acs.jpcc.4c07266","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07266","url":null,"abstract":"The luminescence spectral properties of La_0.95Nd_0.05MnO₃ were investigated upon irradiation with a focused 808 nm CW (continuous wave) laser excitation. An anti-Stokes broadband emission in the visible range centered at 670 nm and a Stokes band in the infrared range centered around 2000 nm were recorded. Their intensities increased exponentially with excitation laser power. The mechanism of laser-induced emission is discussed in terms of an intervalence charge transfer mechanism involving the Mn³⁺–Mn⁴⁺ ionic pair.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"53 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Decoding the Interplay of Hydrogen Bonding, Dispersion, and Steric Interactions in Conformational Isomerism Among Functionalized Pillar[n]arenes","authors":"Ameevardhan Singh Patyal, Joshua D. Howe","doi":"10.1021/acs.jpcc.4c05974","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05974","url":null,"abstract":"Pillar[<i>n</i>]arenes have garnered popularity due to their unique pillar-shaped structure, which results in hydrophobic cavities. These cavities facilitate the formation of inclusion complexes with guest molecules through noncovalent interactions such as π–π stacking, hydrogen bonding, and van der Waals interactions. Such host–guest interactions enable diverse functionalities in pillar[<i>n</i>]arenes, including molecule recognition, self-assembly, and encapsulation. Nevertheless, it is important to note that the host–guest properties of pillar[<i>n</i>]arenes can be influenced by conformational changes, primarily driven by the rotation of hydroquinone units about their methylene bridge axis. These structural changes can lead to variations in underlying noncovalent and steric interactions, impacting the overall stability of the host–guest system and potentially leading to selective uptake of guest molecules. Additionally, due to relative energy differences, we expect a distribution of pillar[<i>n</i>]arene conformations at thermal equilibrium. In this work, we employ density functional theory to evaluate ground-state electronic structures of pillar[<i>n</i>]arene conformations across pillar[<i>n</i>]arenes of various sizes and functionalizations. We have aimed to explore the impact of dispersion interactions, hydrogen bonding, and steric interactions on the overall energetics of pillar[<i>n</i>]arene conformations and determine the dominant conformation at 298 K using a Boltzmann-weighted distribution. The relative strengths of hydrogen bonds across various pillar[<i>n</i>]arene conformations have been examined using Bader’s quantum theory of atoms in molecules topological analysis. Furthermore, we also assessed the solvation of pillar[<i>n</i>]arenes in water using an implicit solvent model that unveils quantitative distinctions in hydrogen bonding and relative dispersion contributions among various pillar[<i>n</i>]arene conformations. Finally, pillar[<i>n</i>]arene conformations with more complex functional groups such as primary amine, alkyl bromide, and carboxylic acid have been studied to evaluate the interplay between underlying interactions such as hydrogen bonding, dispersion, and steric interactions and their collective impact on the structure and energetics of pillar[<i>n</i>]arene conformations.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graphene-Like Linear Dispersion Spin-Gapless Ferromagnetic Half-Metallic in Two-Dimensional DJ Phase Perovskite Cs2M2X8","authors":"Xiao-Xi Yang, Yi Yan, Dan Li","doi":"10.1021/acs.jpcc.4c07635","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07635","url":null,"abstract":"Due to their unique electronic properties, rich regulatory properties, and excellent magnetic response characteristics, two-dimensional (2D) magnetic materials show tremendous application potential in logic computation, information storage, and other fields. However, their practical application has been severely limited by spin polarizability, low Curie temperature, and low magnetic anisotropy in the realm of room-temperature electronics. Therefore, to achieve intrinsic room-temperature ferromagnetism, finding and designing new 2D ferromagnetic materials with robust magnetic order and high Curie temperature has become a research hotspot. Here, through first-principles calculations, the 2D DJ phase Cs₂M₂X₈ (M = Fe, Co, Mn, X = Br, Cl) perovskite is screened by introducing magnetic elements at the M position, and it is found that the 2D Cs₂Mn₂Br/Cl₈ exhibits ferromagnetic half-metal properties. Its two spin channels display zero-gap metallicity and large-band gap semiconductor characteristics, with each Cs₂Mn₂Br/Cl₈ primitive cell having a large magnetic moment of 8 μB. Additionally, the Fermi surface exhibits 100% spin polarization, with neighboring bands displaying graphene-like linear dispersion and an ultrahigh Fermi velocity of 4.73 × 10⁵ m/s, as well as a nodal line semimetal Fermi surface structure, demonstrating excellent transport characteristics in a single spin channel. Moreover, the Curie temperature of the 2D Cs₂Mn₂Br₈ reaches up to 502.8 K, indicating its broad applicability in high-temperature spintronic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Planar Si(IV) of Bis(catecholato)silane on a Metal Surface Induced by a Surface Constraint","authors":"Peizhen Liu, Tiantong Zhang, Jinyu Zhang, Peichao Wang, Hongchao Wang, You Han, Dongbing Zhao, Hong-Ying Gao","doi":"10.1021/acs.jpcc.4c07936","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07936","url":null,"abstract":"The structure of bis(catecholato)silane has been subject to debate, as to whether it is its tetrahedral or planar Si(IV). To tackle the discussion, here, the bis(catecholato)silane molecules with visible molecular-level images on different metal surfaces are investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) simulations. It is found that the bis(catecholato)silane shows a tetrahedral Si(IV) structure on both Au(111) and Ag(111) surfaces, while the bis(catecholato)silane can show a nearly planar Si(IV) structure on the Cu(111) surface due to the strong interaction between the SiO₄ moiety and the metal surface. Naturally, the conformational difference results in the self-assembly and on-surface chemistry behaving differently. Furthermore, the coverage of bis(catecholato)silane influences the self-assembly structures, indicating that the interactions among organic molecules affect the molecular tetrahedral or planar conformations. Our study reveals fundamental knowledge of the bis(catecholato)silane molecules on a surface, especially the tetrahedral or planar Si(IV) selectivity influenced by the surface constraint.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"20 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cohesive, Vibrational, and Chemical Bonding Features of 3d- and 4d-Transition Metal MX (X = C, N) Compounds: A Systematic Approach","authors":"Dalía S. Bertoldi, A. Fernández Guillermet","doi":"10.1021/acs.jpcc.4c07357","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07357","url":null,"abstract":"The paper presents an ab initio approach to the cohesive, vibrational, and phase stability properties of the MX (cF8) NaCl-type structure compounds formed by M = Sc to Ni of the 3d-transition-metal series and M = Y to Pd of the 4d-transition-metal series, with X = C and N. The cohesive energy (<i>E</i>_coh) and a characteristic energy [<i>E</i>(0)] related to the vibrational entropy show a well-defined pattern of covariation with the average number of electrons per atom of the compound (<i>n</i>_e). Various types of homologous behavior of compounds formed by 3d- and 4d-elements from the same group of the periodic table are detected. In particular, a striking covariation of the <i>E</i>_coh [and <i>E</i>(0)] values for MX compounds formed by the pairs of elements Sc/Y to Ni/Pd with the increase in <i>n</i>_e is established. These various systematic findings are discussed in terms of chemical bonding features of the compounds, which include the hybridization of the p-electron states of C (or N) with the d-states of the transition metals. Using systematic calculations of the crystal Hamiltonian populations, a comprehensive explanation is developed, which relies on the progressive occupation of bonding and antibonding electronic orbitals.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"30 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tritium Accommodation and Diffusion in Li8PbO6 from First-Principles Simulations","authors":"Andrew W. Davies, Samuel T. Murphy","doi":"10.1021/acs.jpcc.4c08016","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08016","url":null,"abstract":"Li₈PbO₆ has been proposed as an alternative candidate breeding blanket material for use in fusion reactors. As lithium is burned inside the blanket, tritium is produced within the ceramic matrix until it reaches the surface, from where it is recovered by isotope exchange reactions. To fully understand the tritium recovery process, it is essential to understand how tritium is accommodated in the fuel and subsequently migrates to the surface. Therefore, in this work, we employ density functional theory (DFT) to examine tritium accommodation in Li₈PbO₆. We then used the nudged elastic band (NEB) method to understand the mechanisms for the migration of tritium-accommodating defects in Li₈PbO₆. We have found tritium is more likely bind to an oxygen ion and form a hydroxyl than exist in the traditional interstitial sites. We predict the barriers for migration of tritium interstitials to be anisotropic, with barriers of 0.27 and 0.69 eV along the <i>xy</i>-plane and through the <i>z</i>-axis, respectively. The barrier for escape from a lithium vacancy trapping site we found to be in the range of 0.76–0.85 eV, and an activation energy range of 0.67–1.18 eV for the migration of the trapping site as a whole. Due to the low migration energies found, we predict that aging of the blanket will have a lower significance on tritium release compared to other leading candidate materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}