The Journal of Physical Chemistry A最新文献

{"title":"A Tribute to Alec M. Wodtke","authors":"Hua Guo*, Gerard Meijer* and Xueming Yang*, ","doi":"10.1021/acs.jpca.5c0132210.1021/acs.jpca.5c01322","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01322https://doi.org/10.1021/acs.jpca.5c01322","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 13","pages":"2973–2975 2973–2975"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758811","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":"Looking Backward and Forward","authors":"Alec Wodtke*, ","doi":"10.1021/acs.jpca.5c0132410.1021/acs.jpca.5c01324","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01324https://doi.org/10.1021/acs.jpca.5c01324","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 13","pages":"2976–2987 2976–2987"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758808","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":"Numerical Calculations of Electric Response Properties Using the Bubbles and Cube Framework.","authors":"Eelis Solala, Wen-Hua Xu, Pauli Parkkinen, Dage Sundholm","doi":"10.1021/acs.jpca.5c00849","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00849","url":null,"abstract":"<p><p>We have developed a fully numerical method for calculating the response of the Hartree-Fock orbitals to an external electric field. The Hartree-Fock orbitals are optimized using Green's function methods by iterative numerical integration of the convolution with the Helmholtz kernel. The orbital response is obtained analogously by iterative numerical integration of the convolution with the Helmholtz kernel of the Sternheimer equation. The orbitals are expanded in atom-centered functions (bubbles), consisting of numerical radial functions multiplied by spherical harmonics. The remainder, i.e., the difference between the bubble expansion and the exact orbitals, is expanded in numerical tensorial local basis functions on a three-dimensional grid (cube). The methods have been tested by calculating polarizabilities for He, H₂, and NH₃, which are compared to the literature values.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762601","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":"First-Generation Products of <i>Trans</i>-2-Hexenal Ozonolyis: A New Look at the Mechanism.","authors":"Najoua Derbel, Alexander Alijah, Struan H Robertson, Thomas Lauvaux, Lilian Joly","doi":"10.1021/acs.jpca.4c07608","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07608","url":null,"abstract":"<p><p>The ozonolysis reaction of <i>trans</i>-2-hexenal was studied theoretically on the basis of highly accurate CCSD(T)-F12b/AVTZ energy values obtained in M06-2X/AVTZ preoptimized nuclear configurations. The kinetics was modeled with the help of the master equation solver MESMER. Apart from the expected stable oxidation products 1-butanal (17%) and glyoxal (35%), a secondary ozonide is formed on the glyoxal channel, which is the principal first-generation product (49%). It is further shown that glyoxal is created on two competing pathways, one of which leads to simultaneous production of the ester propylformate (18%). The inclusion of all of these mechanisms explains the experimental findings and identifies for the first time the origin of the experimental carbon deficit.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762583","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":"Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations.","authors":"Sebastian Riis Thomsen, Nicolai Machholdt Høyer, Mads Greisen Højlund, Ove Christiansen","doi":"10.1021/acs.jpca.4c07704","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07704","url":null,"abstract":"<p><p>The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762585","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":"Experimental and Theoretical Investigation of 2-Methylbenzothiazole Oxidation by OH in Air and the Role of O₂ and NO.","authors":"Weihong Wang, Natalia V Karimova, R Benny Gerber, Barbara J Finlayson-Pitts","doi":"10.1021/acs.jpca.5c00826","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00826","url":null,"abstract":"<p><p>Benzothiazoles are in widespread use as components of, or precursors to, a variety of consumer and industrial products. This class of compounds encompasses the simplest molecule benzothiazole (BTH) in which a benzene ring is fused to a thiazole ring, as well as a series of derivatives which are commonly functionalized at the C2 position of the thiazole ring. The addition of groups at this position modifies the reactivity in ways that are not well-known. While the reactions of benzothiazoles in water have been the subject of investigation, in part for wastewater treatment applications, much less is known about their atmospheric reactions where gas phase oxidation by the OH radical is expected to dominate. We report here studies of the kinetics, products, and mechanism of reaction of 2-methylbenzothiazole (MeBTH) with OH in the gas phase using a combination of experiments and theory. Comparison to previous studies of the OH oxidation of BTH highlights the impact of substitution of a methyl group at the 2-position on the products and reactivity. Specifically, the rate constant at 298 K and 1 atm pressure for the MeBTH-OH reaction is (3.0 ± 0.4) × 10^-12 cm³ molecule^-1 s^-1 (1σ), about 50% faster than that of BTH. In addition, attack of OH on the -CH₃ group at the 2-position of the thiazole ring to form the aldehyde as the stable product becomes important, accounting for ∼ 33% of the overall reaction. Formation of the phenol-type products from attack on the benzene ring accounts for the remainder, with the experimental relative yields consistent with theoretical predictions based on energies of formation of the prereaction MeBTH···OH complex. The formation of the aldehyde product (2-CHO-BTH) involves a sequence of five distinct stages involving two oxygen molecules and one NO. Both processes involve a spin flip of unpaired electrons, which enables a transition between electronic states that is essential for the reaction to proceed. Using the room temperature rate constant, the estimated lifetimes of MeBTH in air range from about 9 h to 4 days over OH concentrations of 10⁷ - 10⁶ cm^-3. Thus, this reaction represents a significant loss process for MeBTH in air both outdoors and indoors, and exposures and toxicity of both the parent MeBTH and its oxidation products need to be taken into account in assessments of its environmental fates.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750290","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":"Evaluation of Diffuse Basis Sets for Simulations of Strong Field Ionization Using Time-Dependent Configuration Interaction with a Complex Absorbing Potential.","authors":"Andrew S Durden, H Bernhard Schlegel","doi":"10.1021/acs.jpca.5c00195","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00195","url":null,"abstract":"<p><p>For simulations of strong field ionization using time-dependent configuration with a complex absorbing potential (TDCI-CAP), standard molecular basis set must be augmented by several sets of diffuse functions to support the wave function as it is distorted by the strong field and interacts with the absorbing potential. Various sets of diffuse functions used in previous studies have been extended and evaluated for their ability to model the angular dependence of the strong field ionization. These sets include diffuse <i>s</i>, <i>p</i>, <i>d</i>, and <i>f</i> Gaussian functions with selected even-tempered exponents of the form 0.0001 × 2<i>ⁿ</i> placed on each atom. For single-centered test cases, the largest contribution to the ionization rate is from functions with a maximum in the radial distribution close to the onset of the complex absorbing potential, while functions with smaller exponents also contributed to the rate. For molecules, diffuse functions on adjacent centers overlap strongly, leading to linear dependencies. The transformation to remove these linear dependencies mixes functions of different angular momenta making it difficult to assess the importance of individual <i>s</i>, <i>p</i>, <i>d</i>, and <i>f</i> functions in simulating the rate for molecules. As an alternative, a hierarchy of diffuse basis sets was constructed by starting with a small set and adding one or two functions at a time. These basis sets were evaluated for their ability to reproduce the rate and shape of the angular dependence of strong field ionization. When combined with the aug-cc-pVTZ molecular basis set and an absorbing potential starting at 3.5 times the van der Waals radius for each atom, the most diffuse <i>s</i>, <i>p</i>, <i>d</i>, and <i>f</i> functions need to have exponents of 0.0032, 0.0032, 0.0064, and 0.0064, respectively, or smaller. Strong field ionization from electronegative atoms such as oxygen required additional <i>f</i> functions with tight exponents of 0.0512 and 0.1024. Diffuse basis sets that perform well for the angular dependence of the ionization rate with a static field are equally effective for strong field ionization with a linearly polarized 7-cycle 800 nm pulse.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762579","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":"Oligothiophene-Based Photovoltaic Materials for Organic Solar Cells: Exciton Properties by the CNDOL Fockian Approach.","authors":"Alberto Guerra-Barroso, Yoana Pérez-Badell, Ana L Montero-Alejo, Luis A Montero-Cabrera","doi":"10.1021/acs.jpca.4c07959","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07959","url":null,"abstract":"<p><p>In this study, we apply the CNDOL/2SS approximate Fockian with the configuration interaction of singles (CIS) method to explore the excitonic properties of oligothiophene-based materials for organic solar cells. Our calculations of the excited states and charge density distributions of isolated chromophores and a donor-acceptor pair align closely with experimental data. The methodology used is reliable and useful for addressing complex donor-acceptor systems and their eventual design. The prediction of exciton binding energy using the Coulomb and exchange (<i>E</i>^CE) term of the CIS energy transitions, combined with charge density difference maps to visualize the electronic structure of excitons, aids in distinguishing charge transfer states between multiple transitions present in the molecular aggregates representing the donor-acceptor pair. Our results indicate that the donor-acceptor blend Tz6T:eC9-4F exhibits strong low-energy light absorption and a state alignment that enables barrier-free charge transport. The sandwich-type arrangement of this pair reveals a charge transfer (CT) state characterized by low exciton binding energy (low <i>E</i>^CE term), highlighting its potential for optimizing organic solar cell performance. In contrast, less-ordered arrangements of the donor-acceptor pair show CT states at higher energies, which may compete with other deactivation processes and reduce the efficiency. This study provides a cost-effective approach to predicting and interpreting the feasibility of charge transfer in molecular aggregate designs for solar cells.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762611","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":"Electronic Instability and Solvation Stabilization of Oxocarbon Dianions (C_<i>n</i>O_<i>n</i>)^2- (<i>n</i> = 4-6).","authors":"Wenjin Cao, Xue-Bin Wang","doi":"10.1021/acs.jpca.5c01355","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01355","url":null,"abstract":"<p><p>Oxocarbon dianions (C_<i>n</i>O_<i>n</i>)^2- have been recently found to be promising candidates in the design of high-capacity and fast rechargeable batteries but are intrinsically unstable in the isolated form. Fundamental understandings of their electronic structures, solvent stabilization, and interactions with solvents and counterions are crucial in comprehending their electron transfer reactions occurring in batteries. In this article, we employed microsolvated dianionic clusters as models and combined negative ion photoelectron spectroscopy (NIPES) and theoretical computations to probe the electronic instability and solvation stabilization of (C_<i>n</i>O_<i>n</i>)^2- (<i>n</i> = 4-6) dianions. Through the smallest observable members in each series of microhydrated dianions and their recorded adiabatic and vertical detachment energies (ADEs and VDEs), the minimum numbers of H₂O molecules required to stabilize (C_<i>n</i>O_<i>n</i>)^2- dianions are determined to be 4, 3, and 2 for <i>n</i> = 4, 5, and 6, respectively, while 3 and 2 water molecules can make (C₄O₄)^2- and (C₅O₅)^2- metastable and detectable. Using theoretical calculations, we determined the lowest energy structures of each complex. The first few H₂O molecules prefer to be directly hydrogen bonded to two adjacent O atoms around the oxocarbon ring. The water binding strengths are generally comparable when each H₂O molecule is bound at a separate binding pocket, but the binding strengths decrease when all binding pockets are occupied, in parallel with the observed ADE and VDE shift trends. Moreover, hydrated (C₄O₄)^2- dianions are found to possess distinct electronic structures compared to its (C₅O₅)^2- and (C₆O₆)^2- analogues due to its near-degenerate HOMO and HOMO-1, while there exists a larger gap for the latter two dianions. Upon hydration, the overall electronic structure patterns are maintained without much distortion, but fine changes are noticeable, which warrant future studies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762575","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":"Binding Motifs of Doubly and Singly Charged Proton-Bound Clusters of B₁₂F₁₂^2- and Diaminoalkanes.","authors":"Arthur E Lee, Patrick Thomas, Courtney Kates, Terrance B McMahon, W Scott Hopkins","doi":"10.1021/acs.jpca.4c08341","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08341","url":null,"abstract":"<p><p>The complexation of perfluorinated dodecaborate, B₁₂F₁₂^2-, with protonated diaminoalkanes, [H₂N(CH₂)<i>_n</i>H₂N] (<i>n=</i> 2 - 12), is studied with a combination of infrared multiple photon dissociation (IRMPD) action spectroscopy and ion mobility spectrometry. Singly charged clusters of the form [B₁₂F₁₂ + H₂N(CH₂)<i>_n</i>H₂N + H]^- (<i>n =</i> 2-12) and doubly charged clusters of the form [2B₁₂F₁₂ + H₂N(CH₂)<i>_n</i>H₂N + 2H]^2- (<i>n =</i> 2-12) are observed and characterized experimentally and computationally. For the singly charged clusters, low-energy structural motifs associated with monodentate and bidentate binding motifs of the diaminoalkane are computed via a combination of CREST conformer exploration and density functional theory. For the doubly charged clusters, the doubly protonated diaminoalkane acts as a tether between two B₁₂F₁₂^2- cages. Major product channels of the singly charged and doubly charged species are found to be the formation of HB₁₂F₁₂^- via proton transfer and the loss of B₁₂F₁₂^2-. The fragmentation of HB₁₂F₁₂^- leads to several secondary products, including [B₁₂F₁₁ + N₂]^-. Collision cross sections (CCSs) for the singly charged clusters are reported, and the major subpopulation of the gas phase ensemble for the different singly charged species is the bidentate conformation.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143750287","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}