ACS Physical Chemistry Au最新文献

{"title":"In Spite of the Chemist’s Belief: Metastable Hydrates of CsCl","authors":"Kamila Závacká,&nbsp;Ľubica Vetráková,&nbsp;Johannes Bachler,&nbsp;Vilém Neděla and Thomas Loerting*,&nbsp;","doi":"10.1021/acsphyschemau.4c0009310.1021/acsphyschemau.4c00093","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00093https://doi.org/10.1021/acsphyschemau.4c00093","url":null,"abstract":"<p >In this work, we focus on the low-temperature behavior of concentrated aqueous solutions of cesium chloride and discover two hydrates of CsCl. We employ four different methods, namely, (i) simple cooling at rates between 0.5 and 80 K s^–1, (ii) simple cooling followed by pressurization, (iii) hyperquenching at 10⁶ to 10⁷ K s^–1, and (iv) hyperquenching followed by pressurization. Depending on the method, different types of phase behaviors are observed, which encompass crystallization involving freeze-concentration, pressure-induced amorphization, full vitrification, and polyamorphic transformation. The CsCl hydrates discovered in our work cold-crystallize above 150 K upon heating after ultrafast vitrification (routes iii and iv) and show melting temperatures <i>below</i> the eutectic temperature of 251 K. We determine the composition of these hydrates to be CsCl·5H₂O and CsCl·6H₂O and find evidence for their existence in ESEM, calorimetry, and X-ray diffraction. The dominant and less metastable hydrate is the hexahydrate, where the pentahydrate appears as a minority species. We also reveal the birthplace for the CsCl hydrates, namely, the freeze-concentrated solution (FCS) formed upon cold-crystallization of the fully glassy solution (from iii and iv). The spongy FCS produced upon <i>cooling</i> of the liquid (from i and ii) is incapable of crystallizing CsCl-hydrates. By contrast, the FCS produced upon <i>heating</i> the glassy solution (from iii and iv) shows tiny, fine features that are capable of crystallizing CsCl-hydrates. Our findings contradict the current knowledge that alkali chlorides only have hydrates for the smaller cations Li⁺ and Na⁺, but not for the larger cations K⁺, Rb⁺, and Cs⁺ and pave the way for future determination of CsCl-hydrate crystal structures. The pathway to metastable crystalline materials outlined here might be more generally applicable and found in nature, e.g., in comets or on interstellar dust grains, when glassy aqueous solutions crystallize upon heating.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"195–206 195–206"},"PeriodicalIF":3.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00093","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Per- and Polyfluoroalkyl Substance (PFAS) Degradation in Water and Soil Using Cold Atmospheric Plasma (CAP): A Review","authors":"Victor Somtochukwu Mbanugo,&nbsp;Boluwatife Stephen Ojo,&nbsp;Ta Chun Lin,&nbsp;Yue-Wern Huang,&nbsp;Marek Locmelis and Daoru Han*,&nbsp;","doi":"10.1021/acsphyschemau.4c0009210.1021/acsphyschemau.4c00092","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00092https://doi.org/10.1021/acsphyschemau.4c00092","url":null,"abstract":"<p >Per- and polyfluoroalkyl substances (PFASs) are persistent organic chemicals found in numerous industrial applications and everyday products. The excessive amounts of PFASs in water and soil, together with their link to severe health issues, have prompted substantial public concerns, making their removal from the environment a necessity. Existing degradation techniques are frequently lacking due to their low efficiency, cost-effectiveness, and potential for secondary contamination. Cold Atmospheric Plasma (CAP) technology has emerged as a promising alternative, utilizing energized reactive species to break down PFASs under ambient conditions. Therefore, this review examines the efficacy and effectiveness of CAP in degrading PFASs by reviewing various CAP setups and examining the key factors involved. This review also aims to further the development of CAP as a viable solution for PFAS degradation by addressing outstanding challenges and future directions in soil and water treatment.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"117–133 117–133"},"PeriodicalIF":3.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00092","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Transition State Resonance Radically Reshapes Angular Distributions of the <i>F</i> + <i>H</i> ₂ → <i>FH</i>(<i>v</i> _f = 3) + <i>H</i> Reaction in the 62-102 meV Energy Range.","authors":"Dmitri Sokolovski, Dario De Fazio, Elena Akhmatskaya","doi":"10.1021/acsphyschemau.4c00096","DOIUrl":"10.1021/acsphyschemau.4c00096","url":null,"abstract":"<p><p>Reactive angular distributions of the benchmark <i>F</i> + <i>H</i> ₂(<i>v</i> _i = 0) → <i>FH</i>(<i>v</i> _f = 3) + <i>H</i> reaction show unusual propensity toward small scattering angles, a subject of a long debate in the literature. We use Regge trajectories to quantify the resonance contributions to state-to-state differential cross sections. Conversion to complex energy poles allows us to attribute the effect almost exclusively to a transition state resonance, long known to exist in the <i>F</i> + <i>H</i> ₂ system and its isotopic variant <i>F</i> + <i>HD</i>. For our detailed analysis of angular scattering we employ the package DCS_Regge, recently developed for the purpose [Akhmatskaya E.; Sokolovski D.Comput. Phys. Commun.2022, 277, 108370].</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"219-226"},"PeriodicalIF":3.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11950844/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143754887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Per- and Polyfluoroalkyl Substance (PFAS) Degradation in Water and Soil Using Cold Atmospheric Plasma (CAP): A Review.","authors":"Victor Somtochukwu Mbanugo, Boluwatife Stephen Ojo, Ta Chun Lin, Yue-Wern Huang, Marek Locmelis, Daoru Han","doi":"10.1021/acsphyschemau.4c00092","DOIUrl":"10.1021/acsphyschemau.4c00092","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFASs) are persistent organic chemicals found in numerous industrial applications and everyday products. The excessive amounts of PFASs in water and soil, together with their link to severe health issues, have prompted substantial public concerns, making their removal from the environment a necessity. Existing degradation techniques are frequently lacking due to their low efficiency, cost-effectiveness, and potential for secondary contamination. Cold Atmospheric Plasma (CAP) technology has emerged as a promising alternative, utilizing energized reactive species to break down PFASs under ambient conditions. Therefore, this review examines the efficacy and effectiveness of CAP in degrading PFASs by reviewing various CAP setups and examining the key factors involved. This review also aims to further the development of CAP as a viable solution for PFAS degradation by addressing outstanding challenges and future directions in soil and water treatment.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"117-133"},"PeriodicalIF":3.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11950857/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143754579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Transition State Resonance Radically Reshapes Angular Distributions of the F + H2 → FH(vf = 3) + H Reaction in the 62–102 meV Energy Range","authors":"Dmitri Sokolovski*,&nbsp;Dario De Fazio and Elena Akhmatskaya,&nbsp;","doi":"10.1021/acsphyschemau.4c0009610.1021/acsphyschemau.4c00096","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00096https://doi.org/10.1021/acsphyschemau.4c00096","url":null,"abstract":"<p >Reactive angular distributions of the benchmark <i>F</i> + <i>H</i>₂(<i>v</i>_i = 0) → <i>FH</i>(<i>v</i>_f = 3) + <i>H</i> reaction show unusual propensity toward small scattering angles, a subject of a long debate in the literature. We use Regge trajectories to quantify the resonance contributions to state-to-state differential cross sections. Conversion to complex energy poles allows us to attribute the effect almost exclusively to a transition state resonance, long known to exist in the <i>F</i> + <i>H</i>₂ system and its isotopic variant <i>F</i> + <i>HD</i>. For our detailed analysis of angular scattering we employ the package <span>DCS_Regge</span>, recently developed for the purpose [<contrib-group><span>Akhmatskaya, E.</span>; <span>Sokolovski, D.</span></contrib-group> <cite><i>Comput. Phys. Commun.</i></cite> <span>2022</span>, <em>277</em>, <elocation-id>108370</elocation-id>].</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"219–226 219–226"},"PeriodicalIF":3.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heavy Solution for Molecular Thermal Management: Phonon Transport Suppression with Heavy Atoms","authors":"William Bro-Jørgensen,&nbsp;Andreas Juul Bay-Smidt,&nbsp;Davide Donadio and Gemma C. Solomon*,&nbsp;","doi":"10.1021/acsphyschemau.4c0008410.1021/acsphyschemau.4c00084","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00084https://doi.org/10.1021/acsphyschemau.4c00084","url":null,"abstract":"<p >Thermal management in molecular systems presents challenges that require a deeper understanding of phonon transport, an essential aspect of heat conduction in single-molecule junctions. Our work introduces the use of heavy atoms as a strategy for suppressing phonon transport in organic molecules. Starting with a one-dimensional (1D) force-constant model and density functional theory calculations of model chemical systems, we illustrate how increasing the mass of a central atom affects phonon transmission and conductance. Following this, we turned our attention to the chemically accessible systems of metallapolyynes and extended metal atom chains (EMACs). Our findings suggest that several of the studied EMACs exhibit thermal conductance either near or below a recently proposed threshold of 10 pW/K─a crucial step toward reaching high thermoelectric figure of merits. Specifically, we predict that the molecule MoMoNi(npo)₄(NCS)₂ has a thermal conductance of just 8.3 pW/K at 300 K. Our results demonstrate that conceptually simple chemical modifications can markedly reduce the thermal conductance of single molecules; these results both deepen our understanding of the mechanisms driving single-molecule phonon thermal conductance and suggest a path toward using single molecules as thermoelectric materials.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 2","pages":"162–170 162–170"},"PeriodicalIF":3.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00084","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143696461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Muhammad Usama,&nbsp;Samad Razzaq and Kai S. Exner*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsphyschemau.4c00058","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144412127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Ata Madanchi,&nbsp;Emna Azek,&nbsp;Karim Zongo,&nbsp;Laurent K. Béland,&nbsp;Normand Mousseau and Lena Simine*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsphyschemau.4c00063","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144412129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Chen Zhang*,&nbsp;Valerie A. Niemann,&nbsp;Peter Benedek,&nbsp;Thomas F. Jaramillo and Mathieu Doucet,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsphyschemau.4c00054","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144354720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Mohammad A. Rahman,&nbsp;Mst Nigar Sultana,&nbsp;Daud Sharif,&nbsp;Sultan Mahmud,&nbsp;Justin Legleiter,&nbsp;Peng Li,&nbsp;Blake Mertz* and Stephen J. Valentine*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":3.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsphyschemau.4c00048","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144354721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}