Faraday Discussions最新文献

{"title":"Scattering in extreme environments: general discussion","authors":"Gil Alexandrowicz, Dmitri Babikov, Mark Brouard, Alexander Butler, Helen Chadwick, David W. Chandler, Michal Fárník, Jan Fingerhut, Hua Guo, Tibor Győri, Christian T. Haakansson, Dan J. Harding, Dwayne Heard, Brianna R. Heazlewood, David Heathcote, Nils Hertl, Pablo G. Jambrina, Geert-Jan Kroes, Olivia A. Krohn, Paul D. Lane, Viet Le Duc, Heather J. Lewandowski, Jérôme Loreau, Max McCrea, Kenneth G. McKendrick, Jennifer Meyer, Daniel R. Moon, Amy S. Mullin, Gilbert M. Nathanson, Daniel M. Neumark, Kang-Kuen Ni, Nitish Pal, Eva Pluhařová, Christopher Reilly, Patrick Robertson, Steven J. Sibener, Chris Sparling, Vimala Sridurai, Ajeet Srivastav, Matt Strutton, Arthur G. Suits, Joshua Wagner, Peter D. Watson, Roland Wester, Stefan Willitsch, Alec. M. Wodtke and Bum Suk Zhao","doi":"10.1039/D4FD90018A","DOIUrl":"10.1039/D4FD90018A","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141970078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scattering at condensed-phase surfaces: general discussion","authors":"Daniel J. Auerbach, Dmitri Babikov, Alexander Butler, David W. Chandler, Jan Fingerhut, Hua Guo, Dan J. Harding, David Heathcote, Nils Hertl, Bin Jiang, Geert-Jan Kroes, Paul D. Lane, Jérôme Loreau, Stuart R. Mackenzie, Kenneth G. McKendrick, Daniel R. Moon, Gilbert M. Nathanson, Daniel M. Neumark, Rahul Pandey, George C. Schatz, Steven J. Sibener, Ajeet Srivastav, Claire Vallance, Robert A. B. van Bree, Joshua Wagner, Gilbert C. Walker, Peter D. Watson, Stefan Willitsch, Alec M. Wodtke and Bum Suk Zhao","doi":"10.1039/D4FD90020K","DOIUrl":"10.1039/D4FD90020K","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141915508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scattering of larger molecules – part 2: general discussion","authors":"F. Javier Aoiz, Nadia Balucani, Astrid Bergeat, Alexander Butler, David W. Chandler, Gábor Czakó, Tibor Győri, Dwayne E. Heard, David Heathcote, Brianna R. Heazlewood, Nils Hertl, Pablo G. Jambrina, Ralf I. Kaiser, Olivia A. Krohn, Viet Le Duc, Jérôme Loreau, Stuart R. Mackenzie, Kenneth G. McKendrick, Jennifer Meyer, Gilbert M. Nathanson, Daniel M. Neumark, Rahul Pandey, Christopher Reilly, Patrick Robertson, George C. Schatz, Steven J. Sibener, Arthur G. Suits, Peter D. Watson, Roland Wester, Stefan Willitsch, Alec M. Wodtke and Bum Suk Zhao","doi":"10.1039/D4FD90021A","DOIUrl":"10.1039/D4FD90021A","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141905063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scattering of larger molecules – part 1: general discussion","authors":"Dmitri Babikov, Nadia Balucani, Astrid Bergeat, Mark Brouard, David W. Chandler, Matthew L. Costen, Michal Fárník, Hua Guo, Tibor Győri, Dwayne Heard, David Heathcote, Nils Hertl, Pablo G. Jambrina, Nathanael M. Kidwell, O. A. Krohn, Viet Le Duc, Jérôme Loreau, Stuart R. Mackenzie, Max McCrea, Kenneth G. McKendrick, Jennifer Meyer, Daniel R. Moon, Amy S. Mullin, Gilbert S. Nathanson, Daniel M. Neumark, Kang-Kuen Ni, Martin J. Paterson, Eva Pluhařová, Patrick Robertson, Christopher Reilly, George C. Schatz, Chris Sparling, Arthur G. Suits, Peter D. Watson, Roland Wester, Stefan Willitsch and Alec M. Wodtke","doi":"10.1039/D4FD90019G","DOIUrl":"10.1039/D4FD90019G","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141892341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Concluding remarks: Reflections on the Faraday Discussion on New Directions in Molecular Scattering","authors":"Mark Brouard","doi":"10.1039/D4FD00118D","DOIUrl":"10.1039/D4FD00118D","url":null,"abstract":"<p >These concluding remarks summarize the <em>Faraday Discussion</em> on New Directions in Molecular Scattering. The discussion brought together scientists from a wide range of disciplines, from astrochemistry to coherent quantum control, and the submitted papers highlighted the need for innovation in experimental methods and computational tools to tackle more complex systems, relevant to chemistry in the real world. As recorded in the previous pages of this discussion, the meeting saw lively debate on numerous topical issues. This summary outlines some of the highlighted key developments in the field, and points towards future directions of molecular scattering research.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d4fd00118d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mixed quantum/classical theory (MQCT) approach to the dynamics of molecule–molecule collisions in complex systems†","authors":"Carolin Joy, Bikramaditya Mandal, Dulat Bostan, Marie-Lise Dubernet and Dmitri Babikov","doi":"10.1039/D3FD00166K","DOIUrl":"10.1039/D3FD00166K","url":null,"abstract":"<p >We developed a general theoretical approach and a user-ready computer code that permit study of the dynamics of collisional energy transfer and ro-vibrational energy exchange in complex molecule–molecule collisions. The method is a mixture of classical and quantum mechanics. The internal ro-vibrational motion of collision partners is treated quantum mechanically using a time-dependent Schrödinger equation that captures many quantum phenomena including state quantization and zero-point energy, propensity and selection rules for state-to-state transitions, quantum symmetry and interference phenomena. A significant numerical speed up is obtained by describing the translational motion of collision partners classically, using the Ehrenfest mean-field trajectory approach. Within this framework a family of approximate methods for collision dynamics is developed. Several benchmark studies for diatomic and triatomic molecules, such as H<small>₂</small>O and ND<small>₃</small> collided with He, H<small>₂</small> and D<small>₂</small>, show that the results of MQCT are in good agreement with full-quantum calculations in a broad range of energies, especially at high collision energies where they become nearly identical to the full quantum results. Numerical efficiency of the method and massive parallelism of the MQCT code permit us to embrace some of the most complicated collisional systems ever studied, such as C<small>₆</small>H<small>₆</small> + He, CH<small>₃</small>COOH + He and H<small>₂</small>O + H<small>₂</small>O. Application of MQCT to the collisions of chiral molecules such as CH<small>₃</small>CHCH<small>₂</small>O + He, and to molecule–surface collisions is also possible and will be pursued in the future.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141069804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the chemical dynamics of phenanthrene (C14H10) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C6H5CC) with benzene (C6H6)†","authors":"Shane J. Goettl, Zhenghai Yang, Chao He, Ankit Somani, Adrian Portela-Gonzalez, Wolfram Sander, Alexander M. Mebel and Ralf I. Kaiser","doi":"10.1039/D3FD00159H","DOIUrl":"10.1039/D3FD00159H","url":null,"abstract":"<p >The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction–acetylene addition (HACA) and phenyl addition–dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C<small>₁₄</small>H<small>₁₀</small>)—a three-ring, 14π benzenoid PAH—<em>via</em> a phenylethynyl addition–cyclization–aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C<small>₆</small>H<small>₅</small>CC, X<small>²</small>A<small>₁</small>) with benzene (C<small>₆</small>H<small>₆</small>) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene <em>via</em> indirect scattering dynamics through C<small>₁₄</small>H<small>₁₁</small> intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. This mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141064492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dynamics of carbene formation in the reaction of methane with the tantalum cation in the gas phase†","authors":"Marcel Meta, Maximilian E. Huber, Maurice Birk, Martin Wedele, Milan Ončák and Jennifer Meyer","doi":"10.1039/D3FD00171G","DOIUrl":"10.1039/D3FD00171G","url":null,"abstract":"<p >The controlled activation of methane has drawn significant attention throughout various disciplines over the last few decades. In gas-phase experiments, the use of model systems with reduced complexity compared to condensed-phase catalytic systems allows us to investigate the intrinsic reactivity of elementary reactions down to the atomic level. Methane is rather inert in chemical reactions, as the weakening or cleavage of a C–H bond is required to make use of methane as C<small>₁</small>-building block. The simplest model system for transition-metal-based catalysts is a mono-atomic metal ion. Only a few atomic transition-metal cations activate methane at room temperature. One of the most efficient elements is tantalum, which forms a carbene and releases molecular hydrogen in the reaction with methane: Ta<small>⁺</small> + CH<small>₄</small> → TaCH<small>₂</small><small>⁺</small> + H<small>₂</small>. The reaction takes place at room temperature due to efficient intersystem crossing from the quintet to the triplet surface, <em>i.e.</em>, from the electronic ground state of the tantalum cation to the triplet ground state of the tantalum carbene. This multi-state reactivity is often seen for reactions involving transition-metal centres, but leads to their theoretical treatment being a challenge even today. Chemical reactions, or to be precise reactive collisions, are dynamic processes making their description even more of a challenge to experiment and theory alike. Experimental energy- and angle-differential cross sections allow us to probe the rearrangement of atoms during a reactive collision. By interpreting the scattering signatures, we gain insight into the atomistic mechanisms and can move beyond stationary descriptions. Here, we present a study combining collision energy dependent experimentally measured differential cross sections with <em>ab initio</em> calculations of the minimum energy pathway. Product ion velocity distributions were recorded using our crossed-beam velocity map imaging experiment dedicated to studying transition-metal ion molecule reactions. TaCH<small>₂</small><small>⁺</small> velocity distributions reveal a significant degree of indirect dynamics. However, the scattering distributions also show signatures of rebound dynamics. We compare the present results to the oxygen transfer reaction between Ta<small>⁺</small> and carbon dioxide, which we recently studied.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d3fd00171g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141064490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bimolecular collision outcomes on multidimensional potential energy surfaces: infrared spectroscopy and activation of NO–alkane collision complexes","authors":"John P. Davis, P. Garrett Burroughs, W. Churchill Wilkinson, Ellora Majumdar and Nathanael M. Kidwell","doi":"10.1039/D3FD00176H","DOIUrl":"10.1039/D3FD00176H","url":null,"abstract":"<p >In bimolecular collisions between open-shell radicals and increasingly-larger alkanes, the relative impact configurations open the possibility of reactive and nonreactive outcomes that are isomer specific. To model the interaction potential between molecular scattering partners, observables are needed from experiments that can quantify both the initial molecular orientations and internal energies on multidimensional potential energy surfaces. Recent work by our group demonstrated that upon infrared (IR) excitation, the dynamics of the nitric oxide–methane collision complex (NO–CH<small>₄</small>) are dependent on the initial monomer geometries, as small changes in configuration substantially affect the energies, electronic couplings, and predissociation pathways due to the Jahn–Teller effect. This study focuses on the isomer-specific scattering mechanisms between NO and ethane (C<small>₂</small>H<small>₆</small>), encoded in the spectroscopic and dynamical signatures of the NO–C<small>₂</small>H<small>₆</small> collision complex. IR action spectroscopy with 1 + 1 resonance-enhanced multiphoton ionization of NO products was employed to characterize the fundamental CH stretch transitions of NO–C<small>₂</small>H<small>₆</small>, as well as to initiate the nonreactive decay mechanisms of the complex. Furthermore, velocity map imaging (VMI) was utilized to explore the dynamics prior to and following IR excitation of NO–C<small>₂</small>H<small>₆</small>, imprinted on the NO photoproducts. This work compares the dynamics from NO–C<small>₂</small>H<small>₆</small> and NO–CH<small>₄</small> vibrational predissociation, in which substantial differences are observed in the energy exchange mechanisms during the evolution of the collision complexes to products.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141064489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Six-dimensional quantum dynamics of an Eley–Rideal reaction between gaseous and adsorbed hydrogen atoms on Cu(111)","authors":"Longlong Xiong, Liang Zhang, Bin Zhao and Bin Jiang","doi":"10.1039/D3FD00163F","DOIUrl":"10.1039/D3FD00163F","url":null,"abstract":"<p >In the form of direct abstraction of a surface adsorbate by a gaseous projectile, the Eley–Rideal (ER) reaction at the gas–surface interface manifests interesting dynamics. Unfortunately, high-dimensional quantum dynamical (QD) studies for ER reactions remain very challenging, which demands a large configuration space and the coordinate transformation of wavefunctions. Here, we report the first six-dimensional (6D) fully coupled quantum scattering method for studying the ER reaction between gas phase H(D) atoms and adsorbed D(H) atoms on a rigid Cu(111) surface. Reaction probabilities and product rovibrational state distributions obtained by this 6D model are found to be quite different from those obtained by reduced-dimensional QD models, demonstrating the high-dimensional nature of the ER reaction. Using two distinct potential energy surfaces (PESs), we further discuss the influence of the PES on the calculated product vibrational and rotational state distributions, in comparison with experimental results. The lateral corrugation and the exothermicity of the PES are found to play a critical role in controlling the energy disposal in the ER reaction.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d3fd00163f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140955242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}