Automated reaction mechanisms and kinetics with the nudged elastic band method‐based AMK_Mountain and its description of the preliminary alkaline hydrolysis of nitrocellulose monomer

• Published in: Journal of Computational Chemistry
• Main Authors: Zhang, Guan, Li, Jin, Liang, Xinxin, Liu, Zongkuan
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 2022
• Subjects: Orca
• Online Access: http://dx.doi.org/10.1002/jcc.26891; https://onlinelibrary.wiley.com/doi/pdf/10.1002/jcc.26891; https://onlinelibrary.wiley.com/doi/full-xml/10.1002/jcc.26891

Abstract To improve the transition state (TS) search capability in complex chemical environments, AMK_Mountain is constructed based on the automated reaction mechanisms and kinetics (AutoMeKin) package. AMK_Mountain does not distinguish the reaction type of the TSs, which is beneficial to obtaining a more comprehensive reaction mechanism. In this study, the first step of the alkaline hydrolysis process of nitrocellulose monomer was adopted as the research object, and 730 possible initial configurations are constructed and 22 TSs pass high‐level calculations. Energy difference and interaction region indicator reveal that the first step of alkaline hydrolysis is mainly the combination of nitrogen‐containing functional groups at the positions α and β with hydroxide anions, followed by the formation of nitric acid and the further loss of protons to form nitrate. Overall, in combination with GFN 2 ‐xTB and ORCA, the AMK_Mountain technique provides a reliable method for the location of the TSs in complex environments.