{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,21]],"date-time":"2026-04-21T23:05:36Z","timestamp":1776812736661,"version":"3.51.2"},"reference-count":80,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2025,7,5]],"date-time":"2025-07-05T00:00:00Z","timestamp":1751673600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPlusChem"],"published-print":{"date-parts":[[2025,8]]},"abstract":"<jats:p>Hydrogen cyanide (HCN) is a chemically and prebiotically important molecule found in the Earth's atmosphere and other planetary environments. Previous photochemical studies have proposed that HCN could originate from reactions between methane photolysis products, such as methyl radical (CH<jats:sub>3<\/jats:sub><jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold>) and triplet methylene (<jats:sup>3<\/jats:sup>CH<jats:sub>2)<\/jats:sub>, and reactive nitrogen species like atomic nitrogen (N) and nitric oxide (NO). In this study, we introduce a new atmospheric route to HCN formation involving the decomposition of CH<jats:sub>2<\/jats:sub>NOX intermediates, which are formed via the recombination of CH<jats:sub>2<\/jats:sub>NO<jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold> with other atmospheric reactive species (X) such as NO, OH<jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold>, and CH<jats:sub>3<\/jats:sub><jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold>. Using high\u2010level quantum chemical calculations [CCSD(T)\/\/M06\u20102X\/6\u2010311++G(3df,3pd)], we investigate the mechanism of CH<jats:sub>2<\/jats:sub>NOX decomposition towards HCN formation via uncatalyzed and catalyst\u2010assisted (H<jats:sub>2<\/jats:sub>O, NH<jats:sub>3<\/jats:sub>, HCl and H<jats:sub>2<\/jats:sub>SO<jats:sub>4<\/jats:sub>) pathways. Kinetic analysis based on transition state theory (TST) reveals that, while CH<jats:sub>2<\/jats:sub>NONO and CH<jats:sub>2<\/jats:sub>NOOH exhibit significant kinetic barriers under ambient conditions, CH<jats:sub>2<\/jats:sub>NOCH<jats:sub>3<\/jats:sub> undergoes rapid decomposition, particularly when catalyzed by H<jats:sub>2<\/jats:sub>SO<jats:sub>4<\/jats:sub>. Among all species examined, the H<jats:sub>2<\/jats:sub>SO<jats:sub>4<\/jats:sub>\u2010assisted decomposition of CH<jats:sub>2<\/jats:sub>NOCH<jats:sub>3<\/jats:sub> shows the highest rate enhancement relative to its uncatalyzed counterpart. This work not only introduces CH<jats:sub>2<\/jats:sub>NO<jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold> as a novel intermediate in atmospheric nitrogen chemistry but also highlights the key role of CH<jats:sub>3<\/jats:sub><jats:bold><jats:sup>\u2022<\/jats:sup><\/jats:bold> (a methane photolysis product) and H<jats:sub>2<\/jats:sub>SO<jats:sub>4<\/jats:sub> in enabling efficient HCN production in both early and modern Earth atmospheres.<\/jats:p>","DOI":"10.1002\/cplu.202500295","type":"journal-article","created":{"date-parts":[[2025,6,14]],"date-time":"2025-06-14T01:14:56Z","timestamp":1749863696000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Computational Investigation of Radical\u2010 and Catalyst\u2010Assisted Decomposition of CH<sub>2<\/sub>NO<b><sup>\u2022<\/sup><\/b> to HCN"],"prefix":"10.1002","volume":"90","author":[{"given":"Sourav","family":"Ghoshal","sequence":"first","affiliation":[{"name":"Department of Chemistry Visva\u2010Bharati University  Santiniketan 731235 India"},{"name":"School of Applied Sciences Kalinga Institute of Industrial Technology (KIIT) Deemed to be University  Bhubaneswar Odisha 751024 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0109-6748","authenticated-orcid":false,"given":"Pranab","family":"Sarkar","sequence":"additional","affiliation":[{"name":"Department of Chemistry Visva\u2010Bharati University  Santiniketan 731235 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,7,5]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.pecs.2007.02.004"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.214.4518.333"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1029\/JC088iC15p10689"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/es061402v"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1029\/JD091iD02p02819"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.epsl.2011.06.011"},{"key":"e_1_2_8_8_1","volume-title":"The Origin of Life","author":"Bernal J. 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