The Journal of Physical Chemistry Letters最新文献_第8页

Estimations of the Activation Energies for the Charge Transfers of the Long-Lived Holes at the Semiconductor/Electrolyte Interfaces of α-Fe2O3 and α-Fe2O3/Co–Pi Photoanodes α-Fe2O3和α-Fe2O3/ Co-Pi光阳极半导体/电解质界面长寿命空穴电荷转移活化能的估计

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-16 DOI: 10.1021/acs.jpclett.5c01803

Seong Kyu Jang, , , Seung Hyeon Jeong, , , Aram Hong, , and , Woon Yong Sohn*,

{"title":"Estimations of the Activation Energies for the Charge Transfers of the Long-Lived Holes at the Semiconductor/Electrolyte Interfaces of α-Fe2O3 and α-Fe2O3/Co–Pi Photoanodes","authors":"Seong Kyu Jang, , , Seung Hyeon Jeong, , , Aram Hong, , and , Woon Yong Sohn*, ","doi":"10.1021/acs.jpclett.5c01803","DOIUrl":"10.1021/acs.jpclett.5c01803","url":null,"abstract":"Cobalt phosphate (Co–Pi) is an efficient co-catalyst known to enhance charge transfer efficiency and lower activation energy, improving photoelectrochemical (PEC) performance. In this study, we estimated the activation energy for hole transfer at the interface between hematite (α-Fe2O3) and Co–Pi. By using a near-field heterodyne transient grating (NF-HD-TG) method, we determined the reaction rate constants for the hole transfer under an applied bias voltage. The activation energy and the pre-exponential factor (A) could be extracted from the temperature-dependent rate constants. After the surface treatment with Co–Pi, the activation energy was significantly reduced from 103.8 to 27.5 kJ/mol. Furthermore, the pre-exponential factor also decreased, indicating that the limited Co–Pi deposition may have reduced the overall active surface area for the water oxidation reaction.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9993–9999"},"PeriodicalIF":4.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5c01803","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accurate, Affordable and Unsupervised: Analytical F12 Gradients Driven by Generalized Internal Coordinates 准确，负担得起和无监督：由广义内坐标驱动的分析F12梯度。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-16 DOI: 10.1021/acs.jpclett.5c02292

Luigi Crisci*, , , Federico Lazzari, , and , Vincenzo Barone*,

{"title":"Accurate, Affordable and Unsupervised: Analytical F12 Gradients Driven by Generalized Internal Coordinates","authors":"Luigi Crisci*, , , Federico Lazzari, , and , Vincenzo Barone*, ","doi":"10.1021/acs.jpclett.5c02292","DOIUrl":"10.1021/acs.jpclett.5c02292","url":null,"abstract":"Accurate yet affordable quantum-chemical predictions are essential in several fields of molecular sciences, such as high-resolution rotational and vibrational spectroscopy. Despite major methodological and technological advances, benchmark-level methods remain prohibitive for molecules of realistic size. We present a modular implementation of the Pisa Composite Schemes (PCS), where analytical gradients ensure robust optimizations and efficient frequency calculations. PCS variants are combined hierarchically to reduce the iterations required in geometry optimizations with the most accurate and costly model, while multilayer ONIOM descriptions extend applicability by treating chemically central regions at high accuracy and peripheral fragments with lower-cost DFT variants. This strategy achieves near-spectroscopic accuracy for medium-sized molecules, including challenging cases such as CN-substituted PAHs and transition states. Freely available and user-friendly, the platform paves the way for routine, spectroscopically accurate simulations of complex systems with quantified uncertainty.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9985–9992"},"PeriodicalIF":4.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068220","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

Multiconfiguration Pair-Density Functional Theory with Quantum Embedding Predicts Correct CO Adsorption Sites on Copper Facets 多组态对密度泛函理论与量子嵌入预测正确的CO吸附位在铜面。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-16 DOI: 10.1021/acs.jpclett.5c02404

Elijah Begin, and , Junwei Lucas Bao*,

{"title":"Multiconfiguration Pair-Density Functional Theory with Quantum Embedding Predicts Correct CO Adsorption Sites on Copper Facets","authors":"Elijah Begin,  and , Junwei Lucas Bao*, ","doi":"10.1021/acs.jpclett.5c02404","DOIUrl":"10.1021/acs.jpclett.5c02404","url":null,"abstract":"The adsorbed states of CO on copper are ubiquitous in copper-mediated heterogeneous catalysis and CO2 reduction, as they represent the initial structures or critical intermediates in reaction mechanisms. However, accurately determining CO adsorption energies and identifying the lowest-energy binding sites on various copper facets present unexpected challenges for density-functional theory with local exchange-correlation functionals. Previous work has shown that all widely used semilocal Kohn–Sham density functionals, including the Perdew–Burke–Ernzerhof (PBE) functional and the M06-L functional, fail to predict the correct, most favorable binding sites of CO on copper surfaces. These functionals consistently favor hollow sites rather than the experimentally observed on-top sites. In this work, we demonstrate that quantum embedded multiconfiguration pair-density functional theory (emb-MC-PDFT), combined with the PBE functional, quantitatively and correctly predicts both the most favorable binding sites and the corresponding binding energies from first-principles for CO adsorption on copper (111), (110), and (100) facets.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9977–9984"},"PeriodicalIF":4.6,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068221","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

Atomic-Level Insight into Ni Clusters Supported on N-Terminated Diamond (111) Surface for HER, OER, and ORR 原子水平的洞察支持Ni簇在n端金刚石（111）表面为HER， OER，和ORR。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-15 DOI: 10.1021/acs.jpclett.5c02155

Wei Cheng, , , Nan Gao*, , , Shaoheng Cheng*, , and , Hongdong Li*,

{"title":"Atomic-Level Insight into Ni Clusters Supported on N-Terminated Diamond (111) Surface for HER, OER, and ORR","authors":"Wei Cheng, , , Nan Gao*, , , Shaoheng Cheng*, , and , Hongdong Li*, ","doi":"10.1021/acs.jpclett.5c02155","DOIUrl":"10.1021/acs.jpclett.5c02155","url":null,"abstract":"Single-cluster catalysts (SCCs), an emerging frontier between single-atom catalysts and conventional metal nanoparticle catalysts, have attracted significant attention due to their unique geometric and electronic structures. Herein, we systematically investigate the structural models and the hydrogen-evolution reaction (HER), oxygen-evolution reaction (OER), and oxygen-reduction reaction (ORR) performances for Nix clusters (x = 2–9) anchored on a N-terminated diamond (111) surface (Nix@ND) through Crystal structure AnaLYsis by Particle Swarm Optimization (CALYPSO)-based structural prediction and density functional theory (DFT) calculations. The Ni–H bonding strength serves as a critical descriptor for HER activity, where a balanced relative strength of ad-/desorption is beneficial for enhancing it. The Gibbs free energy change (ΔG*H) of the Ni7@ND catalyst is −0.25 eV, demonstrating optimal HER performance with an efficiency approaching that of highly efficient Pt-based catalysts. Furthermore, Ni4@ND and Ni2@ND catalysts demonstrate superior OER and ORR performance with low overpotentials (η), which are significantly lower than those of single-atom catalyst Ni1@ND. Volcano curve analysis reveals that the OER performance is maximized at the intermediate adsorption strength of key reaction species (*O, *OH). A pronounced linear correlation is found between ηORR and adsorption energies of intermediate *OH. Furthermore, size effects in SCCs narrow the band gap and increase the number of active sites, thus promoting the catalytic performance (optimizing charge redistribution and reducing the rate-determining step barrier). This design strategy provides atomic-level insights into highly efficient diamond-based SCCs for HER, OER, and ORR.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9946–9955"},"PeriodicalIF":4.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059235","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

Anharmonicity in Molecular Crystals: Generalized Perturbation Theory Meets Periodic Computations 分子晶体中的非调和性：广义微扰理论与周期计算

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-15 DOI: 10.1021/acs.jpclett.5c02217

Davide Mitoli, , , Alessandro Erba, , , Vincenzo Barone, , and , Marco Mendolicchio*,

{"title":"Anharmonicity in Molecular Crystals: Generalized Perturbation Theory Meets Periodic Computations","authors":"Davide Mitoli, , , Alessandro Erba, , , Vincenzo Barone, , and , Marco Mendolicchio*, ","doi":"10.1021/acs.jpclett.5c02217","DOIUrl":"10.1021/acs.jpclett.5c02217","url":null,"abstract":"Accurate simulation of vibrational spectra in the solid state remains a major challenge due to the combined effects of anharmonicity, intermolecular interactions, and resonance phenomena. In this work, we introduce a generalized second-order vibrational perturbation theory (GVPT2) framework for the quantitative computational spectroscopy of molecular solids. The method balances efficiency and accuracy through a perturb-then-diagonalize approach in which resonant terms are excluded in the initial perturbative treatment and subsequently handled more accurately through a variational approach. This strategy ensures numerical stability while capturing essential vibrational couplings. As a representative application, we investigated the infrared spectrum of solid carbon dioxide (dry ice), a prototypical system exhibiting strong anharmonic effects and Fermi resonances. The generalized VPT2 approach accurately reproduces both absolute band positions and splitting patterns, yielding results in excellent agreement with the experimental data. These findings demonstrate the potential of the method for reliable and transferable anharmonic vibrational analysis across a broad class of solid-state systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9956–9962"},"PeriodicalIF":4.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5c02217","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic Insights into Sulfuric Acid Formation in the Atmosphere via First-Principles Simulations 通过第一性原理模拟了解大气中硫酸形成的机理。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-15 DOI: 10.1021/acs.jpclett.5c02165

Manar Al-Kharusi, , , Ali Kachmar*, , , Nidhal Sulaiman, , and , William A. Goddard III,

{"title":"Mechanistic Insights into Sulfuric Acid Formation in the Atmosphere via First-Principles Simulations","authors":"Manar Al-Kharusi, , , Ali Kachmar*, , , Nidhal Sulaiman, , and , William A. Goddard III, ","doi":"10.1021/acs.jpclett.5c02165","DOIUrl":"10.1021/acs.jpclett.5c02165","url":null,"abstract":"Sulfuric acid (H2SO4) is essential in the formation of atmospheric nucleation and cloudy condensation nuclei (CCN). This study uses density functional theory (DFT) to investigate the formation of H2SO4 from sulfur dioxide (SO2) via three key reactions: SO2 oxidation by hydroxyl radicals (R1), reaction of HOSO2 with O2 (R2), and hydrolysis of SO3 with water (R3). Reaction and activation energies were computed using the PBE, r2SCAN, DC-r2SCAN, CAM-B3LYP, and PBE0 flavors of density functional theory. The key findings reveal that reaction R1 has a calculated reaction energy (ΔG) of −23.845 kcal/mol and an activation energy (ΔG*) of −0.628 kcal/mol by using the DC-r2SCAN functional. Reaction R2, which was previously assumed to be barrierless, showed a small but significant activation barrier of 1.225 kcal/mol at the CAM-B3LYP/6-31G** level. Reaction R3 led to a calculated chemical reaction energy of −23.218 kcal/mol, with an activation energy of 5.648 kcal/mol using r2SCAN/TZV2P. This study demonstrates that r2SCAN and DC-r2SCAN provide a computationally efficient alternative to high-level methods, achieving comparable accuracy in the description of sulfuric acid formation.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9939–9945"},"PeriodicalIF":4.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059223","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

High-Efficiency Enrichment of Precious Metals with Mechanochemically Enhanced Galvanic and Kirkendall Effects 利用机械化学强化电偶效应和Kirkendall效应高效富集贵金属

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-15 DOI: 10.1021/acs.jpclett.5c02441

Yuxiang Shi, and , Wei-xian Zhang*,

引用次数: 0

Orbital Alignment as a Key Determinant of Nanotransport in Molecular Tunnel Junctions Despite Fermi Level Pinning: Exponential Correlation with Molecule–Electrode Coupling 尽管费米水平钉钉，轨道对准是分子隧道结中纳米输运的关键决定因素：与分子-电极耦合的指数相关

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-15 DOI: 10.1021/acs.jpclett.5c02168

Ioan Bâldea*, and , Zuoti Xie*,

{"title":"Orbital Alignment as a Key Determinant of Nanotransport in Molecular Tunnel Junctions Despite Fermi Level Pinning: Exponential Correlation with Molecule–Electrode Coupling","authors":"Ioan Bâldea*,  and , Zuoti Xie*, ","doi":"10.1021/acs.jpclett.5c02168","DOIUrl":"10.1021/acs.jpclett.5c02168","url":null,"abstract":"At first glance, interrogating the impact of molecular orbital alignment on charge transport in molecular tunnel junctions may appear out of place, given the well-documented strong Fermi level pinning effect. To demonstrate that the contrary is true, we investigated molecular junctions based on self-assembled monolayers (SAMs) of alkyl monothiols (CnT) and dithiols (CnDT) with Ag, Au, and Pt electrodes using the conducting probe atomic force microscopy (CP-AFM) platform. Analysis of these data reveals that the HOMO–metal electronic coupling Γ and the low bias conductance G are exponentially correlated with the HOMO energy offset relative to the Fermi level ε0 = EMO – EF (Γ ∝ exp(−α̅|ε0|), G ∝ exp(−α|ε0|), α ≈ 2α̅). This impact is remarkably strong: for CnT junctions, a reduction by only 25% in |ε0| translates into an increase of Γ by 1 order of magnitude and of G by 2 orders of magnitude. More broadly, this exponential correlation of Γ and G with ε0 offers deeper insight into nanotransport and extends understanding of the previously reported exponential dependence of Γ and G on the SAM-induced work function shift ΔΦ, which reflects the linear correlation between ε0 and ΔΦ. From a fundamental perspective, it is crucial to highlight that our data validate a formula for Γ (a property which depends on both electrodes of a junction), which features (i) ε0 rather than ΔΦ (i.e., a property of a full junction versus a property of a “half a junction”) and (ii) ε0 rather than its square root in the exponent, thereby invalidating the widely employed tunneling barrier picture.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9963–9971"},"PeriodicalIF":4.6,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059720","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

Plasmonic Properties of Individual Bismuth Nanoparticles 单个铋纳米粒子的等离子体性质。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-13 DOI: 10.1021/acs.jpclett.5c02531

Michael Foltýn, , , Michal Kvapil, , , Tomáš Šikola, , and , Michal Horák*,

引用次数: 0

Temperature-dependent trapping and polaron annihilation on ultrafast time scales in metal-halide perovskites 金属卤化物钙钛矿在超快时间尺度上的温度依赖俘获和极化子湮灭。

IF 4.6 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-09-12 DOI: 10.1021/acs.jpclett.5c02164

Jiacheng Wang, , , Jungmin Park, , , Lei Gao, , , Lucia Di Virgilio, , , Sheng Qu, , , Heejae Kim, , , Hai I. Wang, , , Li-Lin Wu, , , Wen Zeng, , , Mischa Bonn*, , , Zefeng Ren*, , and , Jaco J. Geuchies*,

{"title":"Temperature-dependent trapping and polaron annihilation on ultrafast time scales in metal-halide perovskites","authors":"Jiacheng Wang, , , Jungmin Park, , , Lei Gao, , , Lucia Di Virgilio, , , Sheng Qu, , , Heejae Kim, , , Hai I. Wang, , , Li-Lin Wu, , , Wen Zeng, , , Mischa Bonn*, , , Zefeng Ren*, , and , Jaco J. Geuchies*, ","doi":"10.1021/acs.jpclett.5c02164","DOIUrl":"10.1021/acs.jpclett.5c02164","url":null,"abstract":"Understanding carrier dynamics in photoexcited metal-halide perovskites is key for optoelectronic devices such as solar cells (low carrier densities) and lasers (high carrier densities). Trapping processes at low carrier densities and many-body recombination at high densities can significantly alter the dynamics of photoexcited carriers. Combining optical-pump/THz probe and transient absorption spectroscopy we examine carrier responses over a wide density range (1014–1019 cm–3) and temperatures (78–315 K) in the prototypical methylammonium lead iodide perovskite. At densities below ∼1015 cm–3 (room temperature, sunlight conditions), fast carrier trapping at shallow trap states occurs within a few picoseconds. As excited carrier densities increase, trapping saturates, and the carrier response stabilizes, lasting up to hundreds of picoseconds at densities around ∼1017 cm–3. Above 1018 cm–3 a Mott transition sets in overlapping polaron wave functions leading to ultrafast annihilation, tentatively assigned as an Auger recombination process, occurring over a few picoseconds. We map out trap-dominated, direct recombination-dominated, and Mott-dominated density regimes from 78 to 315 K, ultimately enabling the construction of an electronic “phase diagram”. These findings clarify carrier behavior across operational conditions, aiding material optimization for optoelectronics operating in the low (e.g., photovoltaics) and high (e.g., laser) carrier density regimes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 38","pages":"9925–9932"},"PeriodicalIF":4.6,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.5c02164","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145043462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0