The Journal of Physical Chemistry A最新文献

{"title":"Response of a Tethered Zn-Bis-Terpyridine Complex to an External Mechanical Force: A Computational Study of the Roles of the Tether and Solvent.","authors":"Shouryo Ghose, Anne-Sophie Duwez, Charles-André Fustin, Françoise Remacle","doi":"10.1021/acs.jpca.4c08639","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08639","url":null,"abstract":"<p><p>Polymeric materials containing weak sacrificial bonds can be designed to engineer self-healing and higher toughness, improve melt-processing, or facilitate recycling. However, they usually exhibit a lower mechanical strength and are subject to creep and fatigue. For improving their design, it is of interest to investigate their mechanical response on the molecular scale. We report on a computational study of the response to a mechanical external force of a Zinc(II) bis-methyl phenyl-terpyridine ([Zn-bis-Terpy]²⁺) complex included in a cyclic poly(ethylene glycol) (PEG) tether designed to maintain the two partners of the metal-ligand bonds in close proximity after the rupture of the complex. The mechanical response is studied as a function of the pulling distortion by using the CoGEF isometric protocol, including interactions with a polar solvent (DMSO). We show that tethering favors recombination but destabilizes the complex before bond rupture because of the interactions of the PEG units with Terpy ligands. Similar effects occur between the DMSO molecules and the complex. Our results on the molecular scale are relevant for single-molecule force spectroscopy experiments. Interactions of the complex with solvent molecules and/or with the tether lead to a dispersion of the rupture force values, which could obscure the interpretation of the results.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143778515","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.5c01324","DOIUrl":"https://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"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770748","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":"A Tribute to Alec M. Wodtke","authors":"Hua Guo*,&nbsp;Gerard Meijer* and Xueming Yang*,&nbsp;","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":"Unusual Tautomerism of Methyl Allophanate: Selective Crystallization of the Minor Component via Hydrogen-Bond Network.","authors":"Masashi Hatanaka","doi":"10.1021/acs.jpca.4c08374","DOIUrl":"10.1021/acs.jpca.4c08374","url":null,"abstract":"<p><p>The unexpected tautomerism of methyl allophanates has been observed in the solid state. X-ray analysis, IR/UV spectroscopic data, and density functional theory (DFT) calculations showed that the molecule adopts an imidic form in the crystal, whereas the amide form, which is more stable in aqueous solution, is expected. The imidic form in the solid state is stabilized by a robust hydrogen-bond network, which facilitates the selective isolation of minor imidic species.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3007-3011"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143668491","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":"Ring-Opening Competes with Peroxidation in Fenchone Low-Temperature Autoignition.","authors":"Dario Vassetti, Giorgia Cenedese, Jonathan Honorien, Zeynep Serinyel, Philippe Dagaut, Lydia Boualem, Bruno Moreau, Sandro Gail, Fabrice Foucher, Guillaume Dayma, Andre Nicolle","doi":"10.1021/acs.jpca.4c08396","DOIUrl":"10.1021/acs.jpca.4c08396","url":null,"abstract":"<p><p>We report an atypical competition between fenchyl radical β-scission and peroxidation at low temperatures and unravel the impacts of strain energy and ring substituent location on their respective contributions. Our RRKM modeling reveals that radicals positioned on secondary carbons are the fastest-scission ones, exhibiting maximum local ring relief. Dimethyl substituents contribute to increased local strain compared to norbornane, hindering bridge scission and leading to cyclopentene and isoprene products. The dimethyl corset generates extra torsional strain during HO₂ elimination from QOOH, while ether formation is favored by electron donation from the carbonyl group. The falloff extent is also affected by steric hindrance, insofar as it increases bridge stiffness, leading to a lower vibrational partition function and low-pressure rate constant. Furthermore, methyl-induced restrictions on reactant reorganization are found to modulate an enthalpy-entropy compensation in the Korcek reaction of fenchyl hydroperoxide. Unlike in our previous stirred reactor experiments, the impact of fenchyl peroxidation on reactivity is notable under our new rapid compression machine (RCM) experiments. The present model predicts contrasted fenchyl selectivities with radical position, β-scission and peroxidation prevailing respectively for F₁/F₂/F₃/F₄ and F₅/F₆ radicals. The kinetic mechanism accurately predicts the experimental IDT but indicates a slight first-stage pressure inflection point at the lower experimental temperature, which could not be confirmed experimentally. This new insight into fenchone ring-opening and -closing mechanisms under high-pressure oxidation can be useful for other polycyclic ketones.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3113-3131"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143676647","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":"Improvement of Fourteen Coupled Global Potential Energy Surfaces of ³<i>A'</i> States of O + O₂.","authors":"Xiaorui Zhao, Yinan Shu, Qinghui Meng, Jie J Bao, Xuefei Xu, Donald G Truhlar","doi":"10.1021/acs.jpca.5c00464","DOIUrl":"10.1021/acs.jpca.5c00464","url":null,"abstract":"<p><p>We improved the potential energy surfaces for 14 coupled ³<i>A'</i> states of O₃ by using parametrically managed diabatization by deep neural network (PM-DDNN) with three improvements: (1) We used a new functional form for the parametrically managed activation function, which ensures the continuity of the coordinates used in the parametric management. (2) We used higher weighting for low-lying states to achieve smoother potential energy surfaces. (3) The asymptotic behavior of the coupled potential energy surfaces was further refined by utilizing a better low-dimensional potential. As a result of these improvements, we obtained significantly smoother potentials that are better suited for dynamics calculations. For the new version of 14 coupled ³<i>A'</i> surfaces, the entire set of 532,560 adiabatic energies are fit with a mean unsigned error (MUE) of 45 meV, which is only 0.7% of the mean energy in the data set, which is 6.24 eV.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3166-3175"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661552","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":"Interaction of Small Nitriles Occurring in the Atmosphere of Titan with Metal Ions of Meteoric Origin.","authors":"Hypatia Meraviglia, Jacie Jordan, Camille Foscue, Briawna Stigall, Chance Persons, William S Taylor, Makenzie Provorse Long","doi":"10.1021/acs.jpca.4c08638","DOIUrl":"10.1021/acs.jpca.4c08638","url":null,"abstract":"<p><p>Meteoric material injected into the atmosphere of Titan, Saturn's moon, can react with nitriles and other organic compounds that constitute Titan's atmosphere. However, specific chemical outcomes have not been fully explored. To understand the fates of meteoric metal ions in the Titan environment, reactions of Mg⁺ and Al⁺ with CH₃CN (acetonitrile) and C₂H₅CN (propionitrile) were carried out using a drift cell ion reactor at room temperatures (300 K) and reduced temperatures (∼193 K) and modeled using density functional theory and coupled-cluster theory. Analysis of reactant ion electronic state distributions via electronic state chromatography revealed that Mg⁺ was produced in our instrument exclusively in its ground (²S) state, whereas Al⁺ was produced in both its ¹S ground state and ³P first excited state. Mg⁺(²S) and Al⁺(¹S) produce association products exclusively with both CH₃CN and C₂H₅CN. Primary association reactions with C₂H₅CN occurred with higher reaction efficiencies than those with CH₃CN. Mg⁺(²S) sequentially associates up to four nitrile ligands, and Al⁺(¹S) associates up to three, each via the nitrile nitrogen. Computed binding energies are strongest for the first ligand and diminish with subsequent nitriles. Mg⁺(²S) exhibits a stronger preference for binding nitriles than Al⁺(¹S) because its unpaired electron delocalizes to the nitrile ligands through back-bonding, whereas the lone pair on Al⁺(¹S) remains localized on the metal center. Al⁺(³P) exhibited evidence of bimolecular product formation with both nitriles. Computational modeling of Al⁺(³P) with CH₃CN suggests that the major product, AlCH₃⁺, is kinetically favored over the more energetically stable product, Al⁺(HCN).</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3098-3112"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11973870/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707782","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":"Primary and Secondary Dissociation Pathways in the UV Photochemistry of α-Dicarbonyls.","authors":"Johanna E Rinaman, Craig Murray","doi":"10.1021/acs.jpca.5c00715","DOIUrl":"10.1021/acs.jpca.5c00715","url":null,"abstract":"<p><p>Photolysis of the α-dicarbonyls biacetyl (BiAc, CH₃COCOCH₃) and acetylpropionyl (AcPr, CH₃COCOC₂H₅) following UV excitation to the S₂ state at 280 nm was studied using velocity-map ion imaging. Single-photon VUV ionization at 118 nm was used to detect alkyl and acyl radical photoproducts. Photolysis of BiAc at 280 nm yields the expected Norrish Type I photofragments CH₃ and CH₃CO in a 1.0:1.3 ratio. The CH₃CO speed distribution is bimodal; the fast component is assigned to formation of a CH₃CO fragment pair on the T₁ surface while the slow component most likely results from prompt secondary dissociation of energized CH₃COCO radicals initially produced in conjunction with CH₃, tentatively assigned to dissociation on T₂. AcPr photolysis at 280 nm produces CH₃, CH₃CO and additionally C₂H₅ and C₂H₅CO radicals, with a total alkyl to acyl ratio of 1.0:0.7. Both types of acyl radicals have bimodal speed distributions, which are momentum-matched only for the fast tails. By analogy with BiAc, the fast component is attributed to formation of the CH₃CO + C₂H₅CO pair on the T₁ surface. The slower components are attributed to secondary dissociation of the corresponding energized RCOCO radicals formed in conjunction with the detected alkyl radicals. The results highlight the role that characterization of the detailed partitioning of the available energy can play in identifying mechanisms and quantifying branching between competitive pathways.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3040-3051"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11973875/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707785","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":"Bromine Monoxide Radical Reaction with Propyl-Peroxy and Isopropyl-Peroxy Radicals: Thermokinetic Insights from Cavity Ring-Down Spectroscopy.","authors":"Prasanna Kumar Bej, Balla Rajakumar","doi":"10.1021/acs.jpca.4c07241","DOIUrl":"10.1021/acs.jpca.4c07241","url":null,"abstract":"&lt;p&gt;&lt;p&gt;The experimental rate coefficients for the reaction of bromine monoxide (BrO) with propyl peroxy (PrO&lt;sub&gt;2&lt;/sub&gt;) and isopropyl peroxy (&lt;i&gt;i&lt;/i&gt;-PrO&lt;sub&gt;2&lt;/sub&gt;) radicals were determined using cavity ring-down spectroscopy in the temperature ranges of 263-338 and 253-383 K, respectively. The rate coefficient for the BrO + PrO&lt;sub&gt;2&lt;/sub&gt; was measured to be (1.43 ± 0.14) × 10&lt;sup&gt;-12&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 for the BrO + &lt;i&gt;i&lt;/i&gt;-PrO&lt;sub&gt;2&lt;/sub&gt; as (0.76 ± 0.01) × 10&lt;sup&gt;-12&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 298 K and 95 Torr. The temperature has an inverse effect on the rate coefficients in the studied range, given by &lt;math&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mrow&gt;&lt;mi&gt;B&lt;/mi&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;/mrow&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;263&lt;/mn&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;338&lt;/mn&gt;&lt;mi&gt;K&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/math&gt; = &lt;math&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;2.55&lt;/mn&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;mn&gt;0.92&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/math&gt; × &lt;math&gt;&lt;msup&gt;&lt;mn&gt;10&lt;/mn&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;14&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mi&gt;exp&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;1228.6&lt;/mn&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;mn&gt;244.0&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&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 &lt;math&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mi&gt;k&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mrow&gt;&lt;mi&gt;B&lt;/mi&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;/mrow&gt;&lt;mo&gt;+&lt;/mo&gt;&lt;mi&gt;i&lt;/mi&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;msub&gt;&lt;mrow&gt;&lt;mi&gt;P&lt;/mi&gt;&lt;mi&gt;r&lt;/mi&gt;&lt;mi&gt;O&lt;/mi&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;/msub&gt;&lt;/mrow&gt;&lt;mrow&gt;&lt;mn&gt;253&lt;/mn&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;383&lt;/mn&gt;&lt;mi&gt;K&lt;/mi&gt;&lt;/mrow&gt;&lt;/msubsup&gt;&lt;/math&gt; = &lt;math&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;1.58&lt;/mn&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;mn&gt;0.48&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/math&gt; × &lt;math&gt;&lt;msup&gt;&lt;mn&gt;10&lt;/mn&gt;&lt;mrow&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;mn&gt;14&lt;/mn&gt;&lt;/mrow&gt;&lt;/msup&gt;&lt;mi&gt;exp&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;[&lt;/mo&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;1093.7&lt;/mn&gt;&lt;mo&gt;±&lt;/mo&gt;&lt;mn&gt;147.0&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;mi&gt;T&lt;/mi&gt;&lt;mo&gt;]&lt;/mo&gt;&lt;/mrow&gt;&lt;/math&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;. The rate coefficient was negligibly affected by the pressure variation from 95 to 220 Torr. The multireference theoretical calculations using the CASPT2-F12/AVDZ//M062-X/AVDZ level of theory for the H-abstraction reaction channel were used to determine the electronic energies of all species involved in the reactions. The reaction rate coefficient was calculated by using canonical variational transition (CVT) state theory with small curvature tunneling corrections, yielding results that are in close agreement with the experimentally measured values. At 298 K, the calculated rate coefficient for BrO + PrO&lt;sub&gt;2&lt;/sub&gt; was 1.49 × 10&lt;sup&gt;-12&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;, while for the BrO + &lt;i&gt;i&lt;/i&gt;-PrO&lt;sub&gt;2&lt;/sub&gt;, it was calculated to be 0.83 × 10&lt;sup&gt;-12&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;, which is close to the experimental result within the error limit. The rate coefficient for the recombination reaction of the radicals BrO + PrO&lt;sub&gt;2&lt;/sub&gt; and BrO + &lt;i&gt;i&lt;/i&gt;-PrO&lt;s","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3071-3084"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143690448","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":"Influence of Surfactants with Differently Charged Headgroups on the Surface Propensity of Bromide.","authors":"Shuzhen Chen, Rawan Abouhaidar, Luca Artiglia, Huanyu Yang, Anthony Boucly, Lucia Iezzi, Jérôme Philippe Gabathuler, Thorsten Bartels-Rausch, Céline Toubin, Markus Ammann","doi":"10.1021/acs.jpca.4c07539","DOIUrl":"10.1021/acs.jpca.4c07539","url":null,"abstract":"<p><p>Halide ions in oceans and sea-spray aerosol particles are an important source of reactive halogen species in the atmosphere that impact the ozone budget and radiative balance. The multiphase cycling of halogen species is linked to the abundance of halide ions at the aqueous solution-air interface. Ubiquitously present surface-active organic compounds may affect the interfacial abundance of halide ions. Here, we use liquid jet X-ray photoelectron spectroscopy and molecular dynamics (MD) simulations to assess the impact of surfactants with different headgroups on the abundance of bromide and sodium ions at the interface. Core level spectra of Br 3d, Na 2s, and O 1s are reported for solutions containing tetrabutylammonium, hexylamine (HA), and propyl sulfate. We used a photoelectron attenuation model to retrieve the interfacial concentration of bromide in the presence of these different surfactants. The experimental results confirm the previously reported strong enhancement of bromide in the presence of tetrabutylammonium at the interface. In turn, propyl sulfate had a minor impact on the abundance of bromide but led to a significantly enhanced concentration of sodium cations. The MD simulations performed for bromide solutions containing hexylammonium and propyl sulfate show an enhancement of the interfacial bromide and sodium concentrations, respectively, comparable to the experimental results. The difference between the measured enhancement of bromide for HA and the nearly nonexistent effect of HA on bromide in the MD simulations is ascribed to the small amounts of hexylammonium present in the experimental solution. The present work suggests an important role of electrostatic interactions at the interface, which may guide the assessment of anion and cation abundances in atmospheric particles more generally.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"3085-3097"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11973919/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672940","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}