The Journal of Physical Chemistry A最新文献

{"title":"Exploring Quantum Computing for Metal Cluster Analysis.","authors":"Nia Pollard, A'Laura C Hines, Andre Z Clayborne","doi":"10.1021/acs.jpca.5c01404","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01404","url":null,"abstract":"<p><p>This study explores the application of quantum computing to metal cluster analysis through the development and implementation of a quantum-DFT embedding workflow. Classical computational methods, while transformative, often face limitations in achieving chemical accuracy and computational efficiency, particularly for nanoscale systems. To address these challenges, we integrate the Variational Quantum Eigensolver (VQE) with density functional theory (DFT), leveraging the capabilities of quantum computing aiming to improve the modeling of electronic structures. Aluminum and gold clusters were used as model systems to test the established workflow. The workflow successfully determined electronic properties for aluminum clusters up to Al₇^-. Although gold clusters were used as a test case to investigate the potential reduction of nitric oxide (NO), memory limitations, the lack of relativistic corrections, and the inability to handle open-shell systems presented challenges that underscore the need for advancements in quantum hardware and algorithms. This proof-of-concept study demonstrates the potential of quantum DFT embedding to advance materials discovery, including applications in catalysis and nanomaterial design, while providing insights into the current limitations of near-term quantum devices.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504221","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}

{"title":"Organic Photoredox Catalysts for CO₂ Reduction: Understanding the Mechanisms of Catalyst Deactivation.","authors":"Kaustubh C Rane, Pallavi Sarkar, Shaama Mallikarjun Sharada","doi":"10.1021/acs.jpca.5c03011","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03011","url":null,"abstract":"<p><p>Organic photoredox catalysts, such as terphenyls, offer sustainable alternatives to precious-metal-based catalysts for carbon dioxide utilization. However, their practical application is hindered by low turnover numbers, believed to be caused by rapid catalyst deactivation via reactions, such as Birch reduction. This computational study examines two possible deactivation mechanisms of the three terphenyl isomers: (1) hydrogen atom transfer from an exciplex ([OPP-3^δ--TEA^δ+]*) formed as a result of incomplete excited-state quenching of the catalyst and (2) protonation of the radical anion terphenyl post-quenching by the triethylamine (TEA) radical cation. Calculations reveal that deactivation from the exciplex state is less likely owing to large intrinsic barriers. The TEA radical cation is the most likely proton source for the ground state reaction, and the intrinsic barriers to protonation are lower for the meta- and ortho- isomers compared to the para- isomer. The solvent dielectric plays an important role; exciplex formation is less likely and protonation barriers increase with increasing dielectric. We also identify a computationally accessible descriptor for the terphenyl position(s) that are most susceptible to protonation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511329","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}

{"title":"Classical Nucleation Theory and Tolman Equation in Cluster Thermodynamics: How Small Can They Truly Apply?","authors":"Bin Chen","doi":"10.1021/acs.jpca.5c02843","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02843","url":null,"abstract":"<p><p>Classical nucleation theory and the Tolman equation are two fundamental theories in cluster thermodynamics. Despite their long-standing existence, the applicability of these theories remains questionable. Direct experimental validation is challenging due to the small size of the clusters involved. While theoretical approaches are often used as alternatives, the findings are frequently controversial. In this work, free energy calculations were performed across an unprecedentedly large size range using sophisticated techniques, including aggregation-volume-bias Monte Carlo, for two systems: Lennard-Jones and TIP4<i>P</i>/2005 water. The availability of bulk-phase properties for an infinitely large system (i.e., γ^∞) facilitates a direct comparison to these two theories. The simulation results provide strong support for the applicability of these theories to large clusters, down to those containing a few hundred particles. However, these theories break down for small clusters.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144511328","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}

{"title":"Two-Photon Circular Dichroism in the Algebraic Diagrammatic Construction Framework.","authors":"Antonia Papapostolou, Friederike Schneider, Dirk R Rehn, Andreas Dreuw","doi":"10.1021/acs.jpca.5c02108","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02108","url":null,"abstract":"<p><p>We present the calculation of the rotatory strengths of two-photon circular dichroism (TPCD) in the framework of algebraic diagrammatic construction (ADC) using the intermediate state representation (ISR). First, the differences between the length-gauge formulation of TPCD and three gauge-origin invariant approaches are investigated depending on the order of perturbation theory and the basis set. Subsequently, our ADC/ISR results are compared with results of corresponding coupled cluster methods from the literature. The calculations were performed with the recently published Python package responsefun and show that the user can calculate arbitrary sum-over-states expressions without requiring knowledge of ADC theory. The treatment of response properties with the ADC/ISR approach is computationally feasible up to the third order of perturbation theory, and thus this methodology represents a valuable addition to highly accurate <i>ab initio</i> benchmark methods.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504224","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}

{"title":"","authors":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 25","pages":"XXX-XXX 2305–2315"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jxv129i025_1951723","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144479709","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}

{"title":"","authors":"Yan Feng,&nbsp;Yuting Li,&nbsp;Fang Shen,&nbsp;Haiying Huang,&nbsp;Wenqi Lv,&nbsp;Jinxi Huang and Gang Feng*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 25","pages":"XXX-XXX 2305–2315"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c02440","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144480041","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}

{"title":"","authors":"Megan Woods,&nbsp;Frank A. F. Winiberg,&nbsp;Charles R. Markus,&nbsp;Kristen Zuraski,&nbsp;Robin Shannon,&nbsp;M. Anwar H. Khan,&nbsp;Dudley E. Shallcross,&nbsp;Stanley P. Sander,&nbsp;Mitchio Okumura,&nbsp;Michael McPherson,&nbsp;Sonya Smith and Carl J. Percival*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 25","pages":"XXX-XXX 2305–2315"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c00331","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144480051","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}

{"title":"Pressure, Temperature, and Water Vapor Dependencies of the Bimolecular Rate Coefficients for the Reaction OH + NO + M → HONO + M.","authors":"Megan Woods, Frank A F Winiberg, Charles R Markus, Kristen Zuraski, Robin Shannon, M Anwar H Khan, Dudley E Shallcross, Stanley P Sander, Mitchio Okumura, Michael McPherson, Sonya Smith, Carl J Percival","doi":"10.1021/acs.jpca.5c00331","DOIUrl":"10.1021/acs.jpca.5c00331","url":null,"abstract":"&lt;p&gt;&lt;p&gt;OH+NO is an important termolecular association reaction in the troposphere and stratosphere that influences the atmospheric ozone budget. In this study, rate coefficients for the reaction of OH + NO + &lt;i&gt;M&lt;/i&gt; &lt;b&gt;→&lt;/b&gt; HONO + &lt;i&gt;M&lt;/i&gt; were measured under conditions relevant to the troposphere/lower stratosphere over a temperature range of 228-298 K and pressure range of 50-750 Torr using N&lt;sub&gt;2&lt;/sub&gt; as a bath gas. Time-resolved kinetics were studied by pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) detecting OH by laser-induced fluorescence. Data for the temperature range 258-298 K were fit to two falloff expressions, with the JPL expressions (&lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;N&lt;sub&gt;2&lt;/sub&gt;&lt;/sup&gt; = 7.37 × 10&lt;sup&gt;-31&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-2.90&lt;/sup&gt; cm&lt;sup&gt;6&lt;/sup&gt; molecule&lt;sup&gt;-2&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt; and &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,∞&lt;/sub&gt; = 3.44 × 10&lt;sup&gt;-11&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-0.1&lt;/sup&gt;cm&lt;sup&gt;3&lt;/sup&gt; molecule&lt;sup&gt;-1&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt;) and IUPAC expression (&lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;N&lt;sub&gt;2&lt;/sub&gt;&lt;/sup&gt; = 6.80 × 10&lt;sup&gt;-31&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-2.81&lt;/sup&gt; cm&lt;sup&gt;6&lt;/sup&gt; molecule&lt;sup&gt;-2&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt;, &lt;i&gt;F&lt;/i&gt;&lt;sub&gt;C&lt;/sub&gt; = 0.81, &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,∞&lt;/sub&gt; = 1.96 × 10&lt;sup&gt;-11&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-0.3&lt;/sup&gt; cm&lt;sup&gt;3&lt;/sup&gt; molecule&lt;sup&gt;-1&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt;). At temperatures &lt;i&gt;T&lt;/i&gt; &lt; 258 K, the measured rate coefficients were significantly higher than the IUPAC and JPL fits. To accommodate the rate coefficient deviation from the two expressions, data across the entire temperature range (228-298 K) was fit with two approaches. First, rate coefficients were fit with an empirical modification by adding a second falloff term to the JPL expression with a second low-pressure rate coefficient of &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;N&lt;sub&gt;2&lt;/sub&gt;&lt;/sup&gt; = 5.20 × 10&lt;sup&gt;-35&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-30.4&lt;/sup&gt; cm&lt;sup&gt;6&lt;/sup&gt; molecule&lt;sup&gt;-2&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt;. Second, &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;N&lt;sub&gt;2&lt;/sub&gt;&lt;/sup&gt;, &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,∞&lt;/sub&gt;, and &lt;i&gt;n&lt;/i&gt; were fit globally to the entire temperature data set, but F&lt;sub&gt;C&lt;/sub&gt; was varied for each individual temperature, which increased with decreasing temperature. In the second portion of the study, the influence of H&lt;sub&gt;2&lt;/sub&gt;O on the reaction rate was investigated using a N&lt;sub&gt;2&lt;/sub&gt;-H&lt;sub&gt;2&lt;/sub&gt;O mixture as the bath gas at 50 Torr and 273 and 298 K. The JPL and IUPAC falloff expressions were modified to include H&lt;sub&gt;2&lt;/sub&gt;O as a third-body collisional partner consistent with a nonlinear mixture model. Fits to the data yielded the low pressure termolecular rate coefficients in H&lt;sub&gt;2&lt;/sub&gt;O, &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;H&lt;sub&gt;2&lt;/sub&gt;O&lt;/sup&gt; = 3.81 × 10&lt;sup&gt;-30&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-6.04&lt;/sup&gt; and &lt;i&gt;k&lt;/i&gt;&lt;sub&gt;1,0&lt;/sub&gt;&lt;sup&gt;H&lt;sub&gt;2&lt;/sub&gt;O&lt;/sup&gt; = 3.31 × 10&lt;sup&gt;-30&lt;/sup&gt;(&lt;i&gt;T&lt;/i&gt;/300 K)&lt;sup&gt;-5.81&lt;/sup&gt; cm&lt;sup&gt;6&lt;/sup&gt; molecule&lt;sup&gt;-2&lt;/sup&gt; s&lt;sup&gt;-1&lt;/sup&gt;, respectively. Experimental data were fit using MESMER give energy relaxation parameters of &lt;Δ&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;down,295 K, N2&lt;/s","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"5579-5592"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144264797","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}

{"title":"Vertical Excitation Energies of Organic Molecules Calculated by the MC23 Hybrid Meta On-Top Functional as Compared to Other Multireference Methods.","authors":"Aiswarya M Parameswaran, Dayou Zhang, Donald G Truhlar","doi":"10.1021/acs.jpca.5c02670","DOIUrl":"10.1021/acs.jpca.5c02670","url":null,"abstract":"<p><p>The success of multiconfiguration pair-density functional theory depends on the quality of the on-top functional. We have tested the recently published MC23 hybrid meta on-top pair-density functionals, three other on-top functionals, CASPT2, and XMS-CASPT2 against the benchmark results of Loos et al. [<i>J. Chem. Theory Comput.</i> <b>2020</b>, 16, 1711-1741] for 102 singlet-singlet and 65 singlet-triplet transition excitation energies of organic molecules with 4-6 nonhydrogenic atoms. We find that the tPBE, tPBE0, and MC23 on-top functionals all yield more accurate results on average than CASPT2 by factors of 1.3-1.7. The excitation energies are more accurate for singlet-triplet transitions than for singlet-singlet transitions, and they are more accurate with manually determined active spaces than with automatically generated ones.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"5683-5691"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144309306","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}

{"title":"Tailoring Spectral Response and First Hyperpolarizability of Aryl-Substituted BODIPY-Based 'Push-Pull' Chromophores: Influence of Medium and Structural Modifications.","authors":"Anushree Dutta, Alex Iglesias-Reguant, Josep M Luis, Ramprasad Misra, Nabanita Deb","doi":"10.1021/acs.jpca.5c00383","DOIUrl":"10.1021/acs.jpca.5c00383","url":null,"abstract":"<p><p>The medium plays a pivotal role in dictating the extent of intramolecular charge transfer (ICT) in a molecule, which could be useful in tuning its spectral and nonlinear optical (NLO) response properties. Tuning of ICT in a π-conjugated electronic donor-acceptor molecule has been utilized to modulate the absorption and emission maxima, as well as the first hyperpolarizability (β) of the so-called \"push-pull\" chromophores. Molecules with boron dipyrromethene (BODIPY)-based acceptors became popular in recent years for their unique photophysical properties, ease of synthesis, and high thermal stability. In this article, we present a quantum chemical investigation of the influence of the medium on the ICT process of some novel aryl-substituted BODIPY molecules. This influence ultimately modulates their absorption, emission, and nonlinear optical (NLO) properties. Both static and frequency-dependent β for the second harmonic generation are investigated along with the Pockels effect. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations using the long-range corrected CAM-B3LYP functional were employed in the present study. Restricting the rotation of the aryl ring through the incorporation of methyl groups to the BODIPY moiety enhances the fluorescence decay rate of the molecule. Both electronic and vibrational contributions to the static β are considered. A significant increase in β has been observed in polar solvents, compared to that in the gas phase. An interplay between structural and electronic effects was found to dictate the properties investigated. Our results shed light on the ICT process in the studied BODIPY dyes and could be useful in tuning their spectral properties as well as formulating design principles of novel NLO materials for future technological applications.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"5427-5437"},"PeriodicalIF":2.7,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144092147","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}