{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T18:47:58Z","timestamp":1760122078825,"version":"build-2065373602"},"reference-count":50,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2023,1,11]],"date-time":"2023-01-11T00:00:00Z","timestamp":1673395200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"],"award-info":[{"award-number":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Chongqing Municipal Natural Science Foundation","award":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"],"award-info":[{"award-number":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"]}]},{"DOI":"10.13039\/501100013160","name":"Venture and Innovation Support Program for Chongqing Overseas Returnees","doi-asserted-by":"publisher","award":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"],"award-info":[{"award-number":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"]}],"id":[{"id":"10.13039\/501100013160","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Sichuan Province Science Fund for Distinguished Young Scholars","award":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"],"award-info":[{"award-number":["21973009","92060101","cstc2019jcyj-msxmX0087","cx2021071","2021JDJQ0011"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Symmetry"],"abstract":"<jats:p>The adsorption of silicon tetrachloride (STC, SiCl4) on the silicon surface is a crucial process in polysilicon manufacture. However, the underlying mechanism for the adsorption remains highly uncertain. Here, new dissociative adsorption (DA) reaction pathways involving a flip of a silicon dimer in the first layer and considering physisorption are identified. Different DA patterns, inter-row (IR), inter-dimer (ID), and on-dimer (OD), are confirmed by the density functional theory (DFT) calculations at the PBE-D3(BJ)\/TZVP-MOLOPT-GTH level. The stable structures for all minima are searched by global optimization through the artificial bee colony (ABC) algorithm. Findings reveal that the parent molecules dissociate first by breaking one Si-Cl bond, following which the resulting SiCl3 and Cl fragments are attached to adjacent Si-atom sites. Moreover, dimer flipping significantly reduces the energy barrier for chemisorption, mainly due to the change in electronic structure that enhances the interaction of the site with the SiCl3 radical. Physisorption may also be accompanied by dimer flipping to form a stable adsorption structure.<\/jats:p>","DOI":"10.3390\/sym15010213","type":"journal-article","created":{"date-parts":[[2023,1,12]],"date-time":"2023-01-12T02:28:44Z","timestamp":1673490524000},"page":"213","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Multiple Pathways for Dissociative Adsorption of SiCl4 on the Si(100)-c(4\u00d72) Surface"],"prefix":"10.3390","volume":"15","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5239-334X","authenticated-orcid":false,"given":"Jianxun","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830017, China"},{"name":"Department of Chemistry and Chemical Engineering & Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China"}]},{"given":"Quan","family":"Zhu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830017, China"},{"name":"Department of Chemical Engineering, Sichuan University, Chengdu 610065, China"},{"name":"Engineering Research Center of Combustion and Cooling for Aerospace Power, Sichuan University, Chengdu 610000, China"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2392-8322","authenticated-orcid":false,"given":"Jun","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Engineering & Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China"}]}],"member":"1968","published-online":{"date-parts":[[2023,1,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1625","DOI":"10.1016\/j.rser.2010.11.032","article-title":"A Review of Solar Photovoltaic Technologies","volume":"15","author":"Parida","year":"2011","journal-title":"Renew. Sust. Energy Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1288","DOI":"10.1016\/j.rser.2017.05.019","article-title":"Solar Grade Silicon Production: A Review of Kinetic, Thermodynamic and Fluid Dynamics Based Continuum Scale Modeling","volume":"78","author":"Yadav","year":"2017","journal-title":"Renew. Sust. Energy Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"303","DOI":"10.1007\/s12633-014-9235-x","article-title":"Pathways to Solar Grade Silicon","volume":"7","author":"Andrews","year":"2015","journal-title":"Silicon"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1689","DOI":"10.1021\/acs.jpca.2c00390","article-title":"Theoretical Investigations for Kinetics of the Chemical Reactions: H + SiClx (X = 1, 2, 3)","volume":"126","author":"Zhang","year":"2022","journal-title":"J. Phys. Chem. A"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"859","DOI":"10.1016\/j.rser.2015.09.043","article-title":"Recent Advances in Solar Photovoltaic Systems for Emerging Trends and Advanced Applications","volume":"53","author":"Pandey","year":"2016","journal-title":"Renew. Sust. Energy Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"14504","DOI":"10.1103\/PhysRevB.51.14504","article-title":"Theoretical Study of the Si(100) Surface Reconstruction","volume":"51","author":"Ramstad","year":"1995","journal-title":"Phys. Rev. B"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2636","DOI":"10.1103\/PhysRevLett.68.2636","article-title":"Direct Observation of an Increase in Buckled Dimers on Si(001) at Low Temperature","volume":"68","author":"Wolkow","year":"1992","journal-title":"Phys. Rev. Lett."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"25614","DOI":"10.1021\/jp509095t","article-title":"Dynamics and Energetics of Reconstruction at the Si(100) Surface","volume":"118","author":"Guo","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"201302","DOI":"10.1103\/PhysRevB.83.201302","article-title":"Origin of the Apparent (2\u00d71) Topography of the Si(100)-c(4\u00d72) Surface Observed in Low-Temperature STM Images","volume":"83","author":"Manzano","year":"2011","journal-title":"Phys. Rev. B"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"465","DOI":"10.1016\/j.surfrep.2006.08.002","article-title":"Dissociative Adsorption of Molecular Hydrogen on Silicon Surfaces","volume":"61","year":"2006","journal-title":"Surf. Sci. Rep."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"7950","DOI":"10.1103\/PhysRevB.58.7950","article-title":"Cl2 Dissociation on Si(100)-(2\u00d71) a Statistical Study by Scanning Tunneling Microscopy","volume":"58","author":"Lyubinetsky","year":"1998","journal-title":"Phys. Rev. B"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"443001","DOI":"10.1088\/0953-8984\/21\/44\/443001","article-title":"Competing Interactions in Molecular Adsorption: NH3 on Si(001)","volume":"21","author":"Owen","year":"2009","journal-title":"J. Phys. Condens. Matter"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"174701","DOI":"10.1063\/1.4899841","article-title":"Dissociative Adsorption of CH3X (X = Br and Cl) on a Silicon(100) Surface Revisited by Density Functional Theory","volume":"141","author":"Wang","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"11534","DOI":"10.1021\/ja201060z","article-title":"Multiple Pathways of Dissociative Attachment: CH3Br on Si(100)-2\u00d71","volume":"133","author":"Lim","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1016\/0039-6028(95)01155-2","article-title":"Negative Ion Formation from SiCl4 Adsorbed on Si(100)","volume":"352-354","author":"Guo","year":"1996","journal-title":"Surf. Sci."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/0039-6028(94)91091-X","article-title":"The Adsorption and Surface Reaction of SiCl4 on Si(100)-(2\u00d71)","volume":"302","author":"Gao","year":"1994","journal-title":"Surf. Sci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"186","DOI":"10.1016\/S0039-6028(99)00461-6","article-title":"Theoretical Studies on the Adsorption of SiCl4 on the Si(100) 2\u00d71 Surface","volume":"431","author":"Tossell","year":"1999","journal-title":"Surf. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"12068","DOI":"10.1021\/jp0118874","article-title":"DFT Study of the Adsorption of Chlorosilanes on the Si(100)-2\u00d71 Surface","volume":"105","author":"Hall","year":"2001","journal-title":"J. Phys. Chem. B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"125","DOI":"10.1016\/S0039-6028(99)00610-X","article-title":"SiCl4 Desorption in Chlorine Etching of Si(100)\u2014A First Principles Study","volume":"432","author":"Chan","year":"1999","journal-title":"Surf. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1016\/j.apsusc.2018.12.253","article-title":"Molecular Adsorption and Surface Formation Reactions of HCl, H2 and Chlorosilanes on Si(100)-c(4\u00d72) with Applications for High Purity Silicon Production","volume":"475","author":"Yadav","year":"2019","journal-title":"Appl. Surf. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"9901","DOI":"10.1063\/1.1329672","article-title":"A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths","volume":"113","author":"Henkelman","year":"2000","journal-title":"J. Chem. Phys."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"L789","DOI":"10.1016\/S0039-6028(00)00757-3","article-title":"A Channel for Dimer Flipping on the Si(001) Surface","volume":"465","author":"Hwang","year":"2000","journal-title":"Surf. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"3084","DOI":"10.1103\/PhysRevLett.86.3084","article-title":"Atomically Resolved Local Variation of the Barrier Height of the Flip-Flop Motion of Single Buckled Dimers of Si(100)","volume":"86","author":"Hata","year":"2001","journal-title":"Phys. Rev. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"136101","DOI":"10.1103\/PhysRevLett.106.136101","article-title":"Toggling Bistable Atoms Via Mechanical Switching of Bond Angle","volume":"106","author":"Sweetman","year":"2011","journal-title":"Phys. Rev. Lett."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"506","DOI":"10.1126\/science.290.5491.506","article-title":"Dimer Preparation That Mimics the Transition State for the Adsorption of H2 on the Si(100)-2\u00d71 Surface","volume":"290","year":"2000","journal-title":"Science"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"24800","DOI":"10.1021\/jp207580v","article-title":"Influence of Flipping Si Dimers on the Dissociation Pathways of Water Molecules on Si(001)","volume":"115","author":"Yu","year":"2011","journal-title":"J. Phys. Chem. C"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1038\/nnano.2008.65","article-title":"Dipole-Directed Assembly of Lines of 1,5-Dichloropentane on Silicon Substrates by Displacement of Surface Charge","volume":"3","author":"Harikumar","year":"2008","journal-title":"Nat. Nanotechnol."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"24173","DOI":"10.1039\/C5CP04060D","article-title":"Abcluster: The Artificial Bee Colony Algorithm for Cluster Global Optimization","volume":"17","author":"Zhang","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"3003","DOI":"10.1039\/C5CP06313B","article-title":"Global Optimization of Clusters of Rigid Molecules Using the Artificial Bee Colony Algorithm","volume":"18","author":"Zhang","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","article-title":"Generalized Gradient Approximation Made Simple","volume":"77","author":"Perdew","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1787","DOI":"10.1002\/jcc.20495","article-title":"Semiempirical Gga-Type Density Functional Constructed with a Long-Range Dispersion Correction","volume":"27","author":"Grimme","year":"2006","journal-title":"J. Comput. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"194103","DOI":"10.1063\/5.0007045","article-title":"CP2K: An Electronic Structure and Molecular Dynamics Software Package\u2014Quickstep: Efficient and Accurate Electronic Structure Calculations","volume":"152","author":"Iannuzzi","year":"2020","journal-title":"J. Chem. Phys."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"477","DOI":"10.1080\/00268979709482119","article-title":"Hybrid Gaussian and Plane Wave Density Functional Scheme","volume":"92","author":"Lippert","year":"1997","journal-title":"Mol. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"114105","DOI":"10.1063\/1.2770708","article-title":"Gaussian Basis Sets for Accurate Calculations on Molecular Systems in Gas and Condensed Phases","volume":"127","author":"VandeVondele","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1703","DOI":"10.1103\/PhysRevB.54.1703","article-title":"Separable Dual-Space Gaussian Pseudopotentials","volume":"54","author":"Goedecker","year":"1996","journal-title":"Phys. Rev. B"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"4365","DOI":"10.1063\/1.1543154","article-title":"An Efficient Orbital Transformation Method for Electronic Structure Calculations","volume":"118","author":"VandeVondele","year":"2003","journal-title":"J. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"149","DOI":"10.1093\/comjnl\/7.2.149","article-title":"Function Minimization by Conjugate Gradients","volume":"7","author":"Fletcher","year":"1964","journal-title":"Comput. J."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"115425","DOI":"10.1016\/j.mseb.2021.115425","article-title":"Comment on \u201c18 and 12\u2014Member Carbon Rings (Cyclo[N]Carbons)\u2014A Density Functional Study\u201d","volume":"273","author":"Lu","year":"2021","journal-title":"Mater. Sci. Eng. B"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"3825","DOI":"10.1021\/acscatal.7b04195","article-title":"Role of Carbonaceous Aerosols in Catalyzing Sulfate Formation","volume":"8","author":"He","year":"2018","journal-title":"ACS Catal."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"224108","DOI":"10.1063\/5.0004608","article-title":"The Orca Quantum Chemistry Program Package","volume":"152","author":"Neese","year":"2020","journal-title":"J. Chem. Phys."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"98","DOI":"10.1016\/j.chemphys.2008.10.036","article-title":"Efficient, Approximate and Parallel Hartree\u2013Fock and Hybrid DFT Calculations. A \u2018Chain-of-Spheres\u2019 Algorithm for the Hartree\u2013Fock Exchange","volume":"356","author":"Neese","year":"2009","journal-title":"Chem. Phys."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1740","DOI":"10.1002\/jcc.10318","article-title":"An Improvement of the Resolution of the Identity Approximation for the Formation of the Coulomb Matrix","volume":"24","author":"Neese","year":"2003","journal-title":"J. Comput. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"5397","DOI":"10.1063\/1.458517","article-title":"A Simple Measure of Electron Localization in Atomic and Molecular Systems","volume":"92","author":"Becke","year":"1990","journal-title":"J. Chem. Phys."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"270","DOI":"10.1016\/0009-2614(83)80005-0","article-title":"Charge, Bond Order and Valence in the Ab Initio SCF Theory","volume":"97","author":"Mayer","year":"1983","journal-title":"Chem. Phys. Lett."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"539","DOI":"10.1002\/jcc.26812","article-title":"Independent Gradient Model Based on Hirshfeld Partition: A New Method for Visual Study of Interactions in Chemical Systems","volume":"43","author":"Lu","year":"2022","journal-title":"J. Comput. Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"231","DOI":"10.1002\/cmtd.202100007","article-title":"Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions","volume":"1","author":"Lu","year":"2021","journal-title":"Chem. Methods"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"014101","DOI":"10.1063\/1.2408420","article-title":"Canonical Sampling through Velocity Rescaling","volume":"126","author":"Bussi","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"10556","DOI":"10.1021\/acs.jpca.9b07516","article-title":"Orbital-Weighted Dual Descriptor for the Study of Local Reactivity of Systems with (Quasi-) Degenerate States","volume":"123","author":"Inostroza","year":"2019","journal-title":"J. Phys. Chem. A"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1007\/s00894-006-0130-2","article-title":"Halogen Bonding: The \u03c3-Hole","volume":"13","author":"Clark","year":"2007","journal-title":"J. Mol. Model."}],"container-title":["Symmetry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-8994\/15\/1\/213\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T18:03:11Z","timestamp":1760119391000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-8994\/15\/1\/213"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,1,11]]},"references-count":50,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2023,1]]}},"alternative-id":["sym15010213"],"URL":"https:\/\/doi.org\/10.3390\/sym15010213","relation":{},"ISSN":["2073-8994"],"issn-type":[{"type":"electronic","value":"2073-8994"}],"subject":[],"published":{"date-parts":[[2023,1,11]]}}}