{"title":"通过气相质子转移反应优先破坏含nh2复合星际分子","authors":"Robin T. Garrod and Eric Herbst","doi":"10.1039/D3FD00014A","DOIUrl":null,"url":null,"abstract":"<p >Complex, nitrogen-bearing interstellar molecules, especially amines, are targets of particular interest for detection in star- and planet-forming regions, due to their possible relevance to prebiotic chemistry. However, these NH<small><sub>2</sub></small>-bearing molecules are not universally detected in sources where other, oxygen-bearing complex organic molecules (COMs) are often plentiful. Nevertheless, recent astrochemical models have often predicted large abundances for NH<small><sub>2</sub></small>-bearing complex organics, based on their putative production on dust grains. Here we investigate a range of new gas-phase proton-transfer reactions and their influence on the destruction of COMs. As in past studies, reactions between protonated COMs and ammonia (NH<small><sub>3</sub></small>) are found to be important in prolonging gas-phase COM lifetimes. However, for molecules with proton affinities (PA) greater than that of ammonia, proton-transfer reactions result in drastic reductions in abundances and lifetimes. Ammonia acts as a sink for proton transfer from low-PA COMs, while passing on protons to high-PA species; dissociative recombination with electrons then destroys the resulting ions. Species strongly affected include methylamine (CH<small><sub>3</sub></small>NH<small><sub>2</sub></small>), urea (NH<small><sub>2</sub></small>C(O)NH<small><sub>2</sub></small>) and others bearing the NH<small><sub>2</sub></small> group. The abundances of these species show a sharp time dependence, indicating that their detectability may rest on the precise chemical age of the source. Rapid gas-phase destruction of glycine (NH<small><sub>2</sub></small>CH<small><sub>2</sub></small>COOH) in the models suggests that its future detection may be yet more challenging than previously hoped.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":"245 ","pages":" 541-568"},"PeriodicalIF":3.3000,"publicationDate":"2023-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Preferential destruction of NH2-bearing complex interstellar molecules via gas-phase proton-transfer reactions\",\"authors\":\"Robin T. Garrod and Eric Herbst\",\"doi\":\"10.1039/D3FD00014A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Complex, nitrogen-bearing interstellar molecules, especially amines, are targets of particular interest for detection in star- and planet-forming regions, due to their possible relevance to prebiotic chemistry. However, these NH<small><sub>2</sub></small>-bearing molecules are not universally detected in sources where other, oxygen-bearing complex organic molecules (COMs) are often plentiful. Nevertheless, recent astrochemical models have often predicted large abundances for NH<small><sub>2</sub></small>-bearing complex organics, based on their putative production on dust grains. Here we investigate a range of new gas-phase proton-transfer reactions and their influence on the destruction of COMs. As in past studies, reactions between protonated COMs and ammonia (NH<small><sub>3</sub></small>) are found to be important in prolonging gas-phase COM lifetimes. However, for molecules with proton affinities (PA) greater than that of ammonia, proton-transfer reactions result in drastic reductions in abundances and lifetimes. Ammonia acts as a sink for proton transfer from low-PA COMs, while passing on protons to high-PA species; dissociative recombination with electrons then destroys the resulting ions. Species strongly affected include methylamine (CH<small><sub>3</sub></small>NH<small><sub>2</sub></small>), urea (NH<small><sub>2</sub></small>C(O)NH<small><sub>2</sub></small>) and others bearing the NH<small><sub>2</sub></small> group. The abundances of these species show a sharp time dependence, indicating that their detectability may rest on the precise chemical age of the source. Rapid gas-phase destruction of glycine (NH<small><sub>2</sub></small>CH<small><sub>2</sub></small>COOH) in the models suggests that its future detection may be yet more challenging than previously hoped.</p>\",\"PeriodicalId\":76,\"journal\":{\"name\":\"Faraday Discussions\",\"volume\":\"245 \",\"pages\":\" 541-568\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2023-02-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Faraday Discussions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2023/fd/d3fd00014a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Faraday Discussions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2023/fd/d3fd00014a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Preferential destruction of NH2-bearing complex interstellar molecules via gas-phase proton-transfer reactions
Complex, nitrogen-bearing interstellar molecules, especially amines, are targets of particular interest for detection in star- and planet-forming regions, due to their possible relevance to prebiotic chemistry. However, these NH2-bearing molecules are not universally detected in sources where other, oxygen-bearing complex organic molecules (COMs) are often plentiful. Nevertheless, recent astrochemical models have often predicted large abundances for NH2-bearing complex organics, based on their putative production on dust grains. Here we investigate a range of new gas-phase proton-transfer reactions and their influence on the destruction of COMs. As in past studies, reactions between protonated COMs and ammonia (NH3) are found to be important in prolonging gas-phase COM lifetimes. However, for molecules with proton affinities (PA) greater than that of ammonia, proton-transfer reactions result in drastic reductions in abundances and lifetimes. Ammonia acts as a sink for proton transfer from low-PA COMs, while passing on protons to high-PA species; dissociative recombination with electrons then destroys the resulting ions. Species strongly affected include methylamine (CH3NH2), urea (NH2C(O)NH2) and others bearing the NH2 group. The abundances of these species show a sharp time dependence, indicating that their detectability may rest on the precise chemical age of the source. Rapid gas-phase destruction of glycine (NH2CH2COOH) in the models suggests that its future detection may be yet more challenging than previously hoped.