The Journal of Physical Chemistry A最新文献

{"title":"(ZnO)₁₂ Cluster Decorated 2D Porous CN Materials as Efficient Solar Cells.","authors":"Nanshu Liu, Peng Wang, Hengfu Lin, Wei Pei","doi":"10.1021/acs.jpca.4c07535","DOIUrl":"10.1021/acs.jpca.4c07535","url":null,"abstract":"<p><p>Developing high-performance solar cells is a practical way to improve clean energy conversion efficiency. However, the performance of solar cells faces challenges such as fast carrier combination, poor stability, and limited solar light harvesting. Herein, we propose a strategy by decorating periodic holes in two-dimensional (2D) porous carbon-nitrogen (CN) materials with a zero-dimensional (0D) semiconducting (ZnO)₁₂ cluster. The effects of different CN substrates on the photogenerated carrier dynamics and solar cell performance are revealed by first-principles calculations combined with time-dependent <i>ab initio</i> nonadiabatic molecular dynamic (NAMD) simulations. With high structural stabilities, proper energy gaps of 1.81-3.23 eV, and positions, (ZnO)₁₂/CN heterostructures possess enhanced light absorption in the visible region, excellent separation of photogenerated electron-hole pairs with carrier relaxation times of 140-773 ns for electrons and 82-128 ns for holes, and large short-circuit current densities of 15-34 mA cm^-1. The study unveils the fundamental principles for optimizing the solar cell efficiency of metal oxide cluster decorated CN materials in energy conversion.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1616-1622"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062488","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":"Exploring Local Reactivity of Large Systems through Combining Conceptual DFT and the GFN2-xTB Method.","authors":"Ricardo Pino Rios","doi":"10.1021/acs.jpca.4c05879","DOIUrl":"10.1021/acs.jpca.4c05879","url":null,"abstract":"<p><p>This study evaluates the ability of the GFN2-xTB method and Conceptual Density Functional Theory-derived tools to predict local reactivity in large systems. Carbon-based systems such as C₆₀, C₇₀, Li⁺@C₇₀, C₂₄₀, C₃₆₀, C₆₄₈, and C₇₂₀ have been used as test sets, and the orbital-weighted dual descriptor was employed to identify nucleophilic and electrophilic regions, providing a comprehensive analysis of their reactivity patterns. The results confirm that the GFN2-xTB method accurately reproduces reactivity profiles observed experimentally and at the DFT level, particularly in well-known fullerenes like C₆₀ and C₇₀. The addition of an endohedral Li⁺ cation to C₇₀ demonstrated enhanced electrophilicity and reduced unfavorable nucleophilic regions, consistent with previous studies. For larger and less-studied systems, such as C₂₄₀, C₃₆₀, C₆₄₈, and C₇₂₀, the analysis revealed distinct reactivity features, including the localization of nucleophilic regions in -C≡C- units of C₂₄₀/C₆₄₈, the nucleophilic regions at the ends of the C₃₆₀ nanoparticle model, and the emergence of electrophilic zones due to the reduction in aromaticity of the benzenoid rings in C₇₂₀. These findings validate the GFN2-xTB method as a computationally efficient alternative for exploring the reactivity of large structures and contribute valuable insights into their potential applications in molecular design for material science and nanotechnology.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1542-1548"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121870","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":"Energy Response of Atomic and Molecular Orbitals in Nonuniform Magnetic Fields.","authors":"Arun Kantholi, Nikhil Yenugu, Sangita Sen","doi":"10.1021/acs.jpca.4c06769","DOIUrl":"10.1021/acs.jpca.4c06769","url":null,"abstract":"<p><p>The response of atoms and molecules to nonuniform magnetic fields is far less explored than uniform fields. In this work, we analyze the orbital and spin-Zeeman interactions of the electrons with a spatially nonuniform linearly varying magnetic field at the atomic and molecular orbital levels and their role in shaping the net response. Gauge-origin-invariant finite field restricted Hartree-Fock computations are carried out to examine the orbital-Zeeman effect, while the general Hartree-Fock method with a two-component spinor representation of the orbitals helps gauge the combined space-spin response. The nature of degeneracy lifting of the orbitals is found to be distinct from that for uniform fields. Degeneracy lifting of various orbitals by the so-called \"diamagnetic\" <b>A</b>² term is discussed for the first time to the best of our knowledge. A strong directionality of the response is uncovered and explained. Moreover, the role of the reference point for the gradient of the field, which has hitherto been largely ignored, is investigated in detail. The guiding principles for understanding the energy shifts of the atomic and molecular orbitals with change in the reference point are determined, and the minimum energy position and orientation of the ground states of homo- and heterodiatomic molecules relative to the field applied are discussed.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1566-1582"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187618","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":"Identification of Dihydropentalenes as Products of the Molecular-Weight Growth Reaction of Cyclopentadienyl Plus Propargyl.","authors":"Nils Hansen, Nina Gaiser, Thomas Bierkandt, Patrick Oßwald, Markus Köhler, Judit Zádor, Patrick Hemberger","doi":"10.1021/acs.jpca.4c06549","DOIUrl":"10.1021/acs.jpca.4c06549","url":null,"abstract":"<p><p>The resonance-stabilized cyclopentadienyl (C₅H₅) and propargyl (C₃H₃) radicals are important precursors for polycyclic aromatic hydrocarbons (PAHs) and thus play a significant role in molecular-weight growth and soot formation processes under combustion conditions. In this work, we describe an experimental and theoretical investigation of the C₅H₅ + C₃H₃ reaction. Experimentally, we studied this reaction in a resistively heated microtubular SiC reactor at a controlled temperature of ∼1150 K and a pressure of 10-20 mbar. The reactants C₅H₅ and C₃H₃ were pyrolytically generated from anisole (C₆H₅OCH₃) and propargyl bromide (C₃H₃Br). We identified the reactants and the C₈H₈ products isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). The experimentally observed predominant formation of dihydropentalenes over the ring-enlargement reaction to styrene is consistent with our theoretical predictions of the kinetics on the newly calculated C₈H₈ potential energy surface. This work highlights dihydropentalenes as reactants in molecular-weight growth reactions and as potential building blocks in versatile routes for the formation of curved PAHs.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1714-1725"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143070838","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":"Effect of SiO⁺ Rotational Excitation on Dynamics of SiO⁺ + H₂ → SiOH⁺ + H Reaction.","authors":"Tengyu Gao, Ce Liu, Anyang Li","doi":"10.1021/acs.jpca.4c08538","DOIUrl":"10.1021/acs.jpca.4c08538","url":null,"abstract":"<p><p>Quasi-classical trajectory calculations and quantitative trajectory classification using DBSCAN and K-NN algorithms have been employed to study the specifics of the significant promotion of the SiO⁺ + H₂ reaction by high rotational excitation of SiO⁺. There are three different reaction pathways identified. Path-I is a direct reaction process in which the product is formed when H₂ collides with the O atom side of SiO⁺ and the H-H bond breaks. H₂ first collides with the Si atom in path-II, then bounces back, and encounters the O atom to complete the reaction. Path-III is characterized by the formation of an HSiOH⁺ complex, is less affected by rotational excitation, and has the smallest contribution to the entire reaction. At low collision energies, rotational excitation slightly promotes the reaction, possibly due to the coupling of the rotational mode of SiO⁺ and the reaction coordinate of the submerged saddle point. However, this effect weakens with increasing rotational excitation, leading to a complex change in the total integral cross section. Among them, only path-I shows increased reactivity at high rotational excitation. At high collision energies, the integral cross section of the reaction is less sensitive to the rotational quantum number of the reactant, and only a slight increase is observed at the high rotational excitation of SiO⁺.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1682-1687"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187575","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":"OH-Detected Aromatic Microsolvation of an Organic NO Radical: Halogenation Controls the Solvation Side.","authors":"Elisabeth Sennert, Giovanni Bistoni, Martin A Suhm","doi":"10.1021/acs.jpca.4c07744","DOIUrl":"10.1021/acs.jpca.4c07744","url":null,"abstract":"<p><p>The persistent organic radical 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) protects its NO radical center by four methyl groups. Two of them are arranged tightly (t) on one side of the six-membered puckered heterocycle, and the other two more openly (o) on the other side. It is shown by OH stretching infrared spectroscopy in heated supersonic jet expansions that the hydrogen bond and aromatic ring of a first solvating benzyl alcohol have almost no preference for either side. An increased preference for the t side develops in <i>para</i>-halogenated benzyl alcohols, and it is inverted for <i>ortho</i>-halogenated benzyl alcohols. The experimental dependence on the actual halogen (Cl, Br, and I) is weak, whereas different quantum chemical approaches predict more or less pronounced trends along the halogen series. Some of the benzyl alcohol in the pre-expansion reservoir reduces the TEMPO radical to the closed-shell heterocyclic hydroxylamine TEMPO-H (1-hydroxy-2,2,6,6-tetramethylpiperidine), to the extent that the TEMPO-H···TEMPO complex is observed as an impurity.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1648-1658"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11831666/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062426","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":"Toward Explicit Solvation for Simulations of Electrocatalytic Reactions: AIMD for p<i>K</i>_a and Redox Potentials of Transition Metal Compounds and Catalyst Models.","authors":"Gustavo T Feliciano, Alexander A Auer","doi":"10.1021/acs.jpca.4c06898","DOIUrl":"10.1021/acs.jpca.4c06898","url":null,"abstract":"<p><p>In this work, we study the possibility to extend electronic structure simulations for electrocatalysis by explicit solvation models. In previous work, we proposed a simulation scheme that explicitly includes the effects of pH and electrochemical potential in density functional theory (DFT) simulations with implicit solvation. Based on calculations of protonation and oxidation reactions, the pH and electrochemical potential can be included given appropriate reference values. In this work, we compute the p<i>K</i>_a values and oxidation potentials for a series of transition metal aquo complexes and compare the results including implicit, explicit static and explicit dynamic (AIMD) models for the aqueous solvent and compare vs experimental p<i>K</i>_a and redox potential data. This allows the construction of a p<i>K</i>_a/redox potential scale that can in principle be extrapolated to the simulation of other transition metal-based materials. An explicit dynamic solvent model is then proposed and applied to a model system for iridium oxide-based catalysts for the oxygen evolution reaction. We outline the advantages and disadvantages of the different approaches and demonstrate that, at the expense of a larger computational effort, the microsolvation environment of a given model can be described in a robust way using a limited amount of solvent molecules and AIMD. Especially for reactions in which water is solvent and reactant like the oxygen evolution reaction (OER) or oxygen reduction reaction (ORR), this model provides a more detailed and complete description that can be exploited in mechanistic studies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1757-1768"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11831669/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077966","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":"Transformation of Distinct Superatoms to Superalkalis by Successive Ligation of Thymine Nucleobases.","authors":"Wen-Lu Wang, Zhi-Chao Zhang, Shu-Ying Huang, Hai-Yan Zhong, Bi-Lian Ni, Wei-Ming Sun","doi":"10.1021/acs.jpca.4c08440","DOIUrl":"10.1021/acs.jpca.4c08440","url":null,"abstract":"<p><p>The ligation strategy has been widely used in the chemical synthesis of atomically precise clusters. A series of thymine (T)-ligated Al₁₂<i>M</i>-T<i>_n</i> (<i>M</i> = Be, Al, C; <i>n</i> = 1-5) complexes have been studied to reveal the effect of DNA nucleobase ligands on the electronic structures of different superatoms in the present work. In addition to its protective role, the successive attachment of thymine ligands significantly lowers the adiabatic ionization energies (AIEs) of the studied Al₁₂<i>M</i> superatoms with filled and unfilled electronic shells. The continuous decrease in the AIEs of Al₁₂<i>M</i>-T<i>_n</i> is derived from the gradually raised highest occupied molecular orbital (HOMO) levels upon the addition of ligands. Interestingly, the lowering degree of AIEs for such nucleobase-protected superatoms is independent of the distinct shell fillings of Al₁₂<i>M</i> superatoms but is significantly related to the types of nucleobases. Moreover, the obtained Al₁₂<i>M</i>-T₅ superalkalis not only exhibit excellent performance in activating the stable CO₂ and O₂ molecules but also have considerable nonlinear optical (NLO) responses. We, therefore, hope that this study could provide a viable strategy for synthesizing novel nucleobase-ligated superatom clusters with excellent reducing capability to enrich the family of multifunctional nanoclusters.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1673-1681"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062516","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":"Impact of the Criegee Intermediate on the Formation of Secondary Organic Aerosols during E-4-Hexen-1-ol Ozonolysis.","authors":"Meifang Chen, Shengrui Tong, Shanshan Yu, Yanyong Xu, Xiaofan Lv, Hailiang Zhang, Shuai Wang, Maofa Ge","doi":"10.1021/acs.jpca.4c08028","DOIUrl":"10.1021/acs.jpca.4c08028","url":null,"abstract":"<p><p>Criegee intermediates (CIs), which are active species in the troposphere, play an important role in the formation of secondary organic aerosols (SOA). In this study, matrix isolation technology combined with a vacuum Fourier transform infrared spectrometer (MIFT-IR) and smog chamber method were used to study the typical green leaf volatiles (E-4-hexen-1-ol, E4H1O) ozonolysis process. The infrared characteristic peak resulting from the O-O stretching vibration of CH₃CHOO was identified at 882 cm^-1. And the characteristic infrared peaks of CH₂OHCH₂CH₂CHOO were not detected, possibly due to the presence of extremely rapid unimolecular reaction channels. To investigate the subsequent atmospheric reaction process of these two CIs, additional smog chamber experiments with the E4H1O-O₃ system were conducted to investigate the impact on SOA formation mechanisms. The ordered oligomers derived from the continuous oligomerization of RO₂ radicals with several CIs were identified as the primary components of SOA without the addition of sulfur dioxide (SO₂). The addition of SO₂ in the concentration range of 14-159 ppb, acting as a scavenger for CIs, led to the disappearance of the oligomers, while the yield of SOA continued to increase. The reasons for the increased mass concentration of SOA may be a change in the chemical composition. The escalating concentrations of SO₂ underwent reactions with CIs (or OH radicals) to generate H₂SO₄, subsequently elevating the acidity of the particles. The acid particles resulted in the changes in SOA composition, leading to the production of organic sulfates (OSs), thereby contributing to the increase in SOA yield. A number of OSs were detected in the presence of SO₂, which may result from the heterogeneous reaction of oxygen-containing species with sulfuric acid under acidic conditions. Additionally, non-sulfur-containing molecular structures of emerging C_<i>x</i>H_<i>y</i>O_<i>z</i> products in the particle phase were also identified. Our findings provided detailed molecular insights into the mechanism of E4H1O ozonolysis and its impact on SOA formation from the perspective of Criegee chemistry.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1704-1713"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143121879","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":"How Accurate Are QM/MM Models?","authors":"Junming Ho, Haibo Yu, Yihan Shao, Mackenzie Taylor, Junbo Chen","doi":"10.1021/acs.jpca.4c06521","DOIUrl":"10.1021/acs.jpca.4c06521","url":null,"abstract":"<p><p>Despite the success and widespread use of QM/MM methods in modeling (bio)chemically important processes, their accuracy is still not well understood. A key reason is because these methods are ultimately approximations to direct QM calculations of very large systems, which are impractical to perform in most cases. We highlight recent progress toward the development of realistic model systems where it is possible to obtain full QM reference data to directly and systematically evaluate the effectiveness of different QM/MM generation schemes. These model systems are highly flexible and can be tailored to probe the sensitivity of a QM/MM model to different reaction types and simulation parameters such as pairing of QM and MM potentials, QM region size, and composition. It is envisaged that this strategy could be used to directly validate different QM/MM generation schemes and spur the development of more robust models in the future.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1517-1528"},"PeriodicalIF":2.7,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764526","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}