7cbc4b30942ea4ba4d8e187a9b08cf38 pmc_10706303.pdf 725611cbd83c1b8ab3a4dad6ac76c374842a5053 pmc_10706303.pdf 6264ef9afa1c1a4ecc2ec4b5e2bb306e1e8a43a7a8181b8497eccf3f555c5d17 pmc_10706303.pdf Title: Gas-Phase vs. Grain-Surface Formation of Interstellar Complex Organic Molecules: A Comprehensive Quantum-Chemical Study Subject: Several organic chemical compounds (the so-called interstellar complex organic molecules, iCOMs) have been identified in the interstellar medium (ISM). Examples of iCOMs are formamide (HCONH2), acetaldehyde (CH3CHO), methyl formate (CH3OCHO), or formic acid (HCOOH). iCOMs can serve as precursors of other organic molecules of enhanced complexity, and hence they are key species in chemical evolution in the ISM. The formation of iCOMs is still a subject of a vivid debate, in which gas-phase or grain-surface syntheses have been postulated. In this study, we investigate the grain-surface-formation pathways for the four above-mentioned iCOMs by transferring their primary gas-phase synthetic routes onto water ice surfaces. Our objective is twofold: (i) to identify potential grain-surface-reaction mechanisms leading to the formation of these iCOMs, and (ii) to decipher either parallelisms or disparities between the gas-phase and the grain-surface reactions. Results obtained indicate that the presence of the icy surface modifies the energetic features of the reactions compared to the gas-phase scenario, by increasing some of the energy barriers. Therefore, the investigated gas-phase mechanisms seem unlikely to occur on the icy grains, highlighting the distinctiveness between the gas-phase and the grain-surface chemistry. Keywords: astrochemistry; interstellar grains; water ice surfaces; molecule formation; iCOMs; computational chemistry Author: Berta Martínez-Bachs and Albert Rimola Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Mon Nov 27 15:36:17 2023 CET ModDate: Mon Nov 27 16:03:19 2023 CET Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 25 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 4788183 bytes Optimized: no PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- WLENKM+VnURWPalladioL-Bold Type 1 Custom yes yes no 10 0 OFFFCG+VnURWPalladioL Type 1 Custom yes yes no 15 0 YYJSDR+URWPalladioL-Bold Type 1 Custom yes yes no 19 0 KGHRVC+URWPalladioL-Roma Type 1 Custom yes yes no 24 0 FJYUPY+URWPalladioL-Ital Type 1 Custom yes yes no 28 0 NJJAGL+CMSY10 Type 1 Builtin yes yes no 32 0 IRWHZX+TimesNewRomanPSMT Type 1C WinAnsi yes yes 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AFNMDJ+PalatinoLinotype TrueType WinAnsi yes yes no 374 0 AFNMDL+PalatinoLinotype,Italic TrueType WinAnsi yes yes no 377 0 AFNNFF+PalatinoLinotype TrueType MacRoman yes yes no 380 0 Jhove (Rel. 1.28.0, 2023-05-18) Date: 2024-02-02 02:32:31 CET RepresentationInformation: pmc_10706303.pdf ReportingModule: PDF-hul, Rel. 1.12.4 (2023-03-16) LastModified: 2024-01-09 02:28:46 CET Size: 4788183 Format: PDF Version: 1.7 Status: Well-Formed and valid SignatureMatches: PDF-hul MIMEtype: application/pdf PDFMetadata: Objects: 721 FreeObjects: 1 IncrementalUpdates: 0 DocumentCatalog: PageLayout: SinglePage PageMode: UseNone Outlines: Item: Title: Introduction Destination: section.1 Item: Title: Results Destination: section.2 Children: Item: Title: Gas-Phase Reactions Destination: subsection.2.1 Children: Item: Title: Formamide Formation Destination: subsubsection.2.1.1 Item: Title: Acetaldehyde Formation Destination: subsubsection.2.1.2 Item: Title: Methyl Formate Formation Destination: subsubsection.2.1.3 Item: Title: Formic Acid Formation Destination: subsubsection.2.1.4 Item: Title: Reactivity on the Water Ice Surface Models Destination: subsection.2.2 Children: Item: Title: Formamide Formation Destination: subsubsection.2.2.1 Item: Title: Acetaldehyde Formation Destination: subsubsection.2.2.2 Item: Title: Methyl Formate Formation Destination: subsubsection.2.2.3 Item: Title: Formic Acid Formation Destination: subsubsection.2.2.4 Item: Title: Discussion Destination: section.3 Item: Title: Materials and Methods Destination: section.4 Children: Item: Title: Surface Modelling Destination: subsection.4.1 Item: Title: Computatonal Details Destination: subsection.4.2 Item: Title: Conclusions Destination: section.5 Item: Title: Appendix A Destination: section.A. Item: Title: References Destination: section.B. Info: Title: Gas-Phase vs. Grain-Surface Formation of Interstellar Complex Organic Molecules: A Comprehensive Quantum-Chemical Study Author: Berta Martínez-Bachs and Albert Rimola Subject: Several organic chemical compounds (the so-called interstellar complex organic molecules, iCOMs) have been identified in the interstellar medium (ISM). Examples of iCOMs are formamide (HCONH2), acetaldehyde (CH3CHO), methyl formate (CH3OCHO), or formic acid (HCOOH). iCOMs can serve as precursors of other organic molecules of enhanced complexity, and hence they are key species in chemical evolution in the ISM. The formation of iCOMs is still a subject of a vivid debate, in which gas-phase or grain-surface syntheses have been postulated. In this study, we investigate the grain-surface-formation pathways for the four above-mentioned iCOMs by transferring their primary gas-phase synthetic routes onto water ice surfaces. Our objective is twofold: (i) to identify potential grain-surface-reaction mechanisms leading to the formation of these iCOMs, and (ii) to decipher either parallelisms or disparities between the gas-phase and the grain-surface reactions. Results obtained indicate that the presence of the icy surface modifies the energetic features of the reactions compared to the gas-phase scenario, by increasing some of the energy barriers. Therefore, the investigated gas-phase mechanisms seem unlikely to occur on the icy grains, highlighting the distinctiveness between the gas-phase and the grain-surface chemistry. 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