TY - JOUR
T1 - Unveiling the chemical kinetics of aminomethanol (NH2CH2OH)
T2 - insights into (Formula Presented.) H and O2 photo-oxidation reactions and formamide dominance
AU - Nulakani, Naga Venkateswara Rao
AU - Ali, Mohamad Akbar
N1 - Publisher Copyright:
Copyright © 2024 Nulakani and Ali.
PY - 2024
Y1 - 2024
N2 - Aminomethanol is released into the atmosphere through various sources, including biomass burning. In this study, we have expounded the chemical kinetics of aminomethanol in the reaction pathways initiated by the hydroxyl radical ((Formula presented.) H) with the aid of ab initio//density functional theory (DFT) i.e., coupled-cluster theory (CCSD(T))//hybrid-DFT (M06-2X/6-311++G (3df, 3pd). We have explored various possible directions of the (Formula presented.) H radical on aminomethanol, as well as the formation of distinct pre-reactive complexes. Our computational findings reveal that the H transfer necessitates activation energies ranging from 4.1 to 6.5 kcal/mol from the –CH2 group, 3.5–6.5 kcal/mol from the –NH2 group and 7–9.3 kcal/mol from the –OH group of three rotational conformers. The H transfer from –CH2, –NH2 and –OH exhibits an estimated total rate constant (kOH) of approximately 1.97 × 10−11 cm3 molecule−1 s−1 at 300 K. The branching fraction analysis indicates a pronounced dominance of C-centered NH2 (Formula presented.) HOH radicals with a favorability of 77%, surpassing the N-centered (Formula presented.) HCH2OH (20%) and O-centered NH2CH2 (Formula presented.) (3%) radicals. Moreover, our investigation delves into the oxidation of the prominently favored carbon-centered NH2 (Formula presented.) HOH radical through its interaction with atmospheric oxygen molecules. Intriguingly, our findings reveal that formamide (NH2CHO) emerges as the predominant product in the NH2 (Formula presented.) HOH + 3O2 reaction, eclipsing alternative outcomes such as amino formic acid (NH2COOH) and formimidic acid (HN = C(H)-OH). At atmospheric conditions pertinent to the troposphere, the branching fraction value for the formation of formamide is about 99%, coupled with a rate constant of 5.5 × 10−12 cm3 molecule−1 s−1. Finally, we have scrutinized the detrimental impact of formamide on the atmosphere. Interaction of formamide with atmospheric hydroxyl radicals could give rise to the production of potentially perilous compounds such as HNCO. Further, unreacted (Formula presented.) HCH2OH radicals may initiate the formation of carcinogenic nitrosamines when reacting with trace N-oxides (namely, NO and NO2). This, in turn, escalates the environmental risk factors.
AB - Aminomethanol is released into the atmosphere through various sources, including biomass burning. In this study, we have expounded the chemical kinetics of aminomethanol in the reaction pathways initiated by the hydroxyl radical ((Formula presented.) H) with the aid of ab initio//density functional theory (DFT) i.e., coupled-cluster theory (CCSD(T))//hybrid-DFT (M06-2X/6-311++G (3df, 3pd). We have explored various possible directions of the (Formula presented.) H radical on aminomethanol, as well as the formation of distinct pre-reactive complexes. Our computational findings reveal that the H transfer necessitates activation energies ranging from 4.1 to 6.5 kcal/mol from the –CH2 group, 3.5–6.5 kcal/mol from the –NH2 group and 7–9.3 kcal/mol from the –OH group of three rotational conformers. The H transfer from –CH2, –NH2 and –OH exhibits an estimated total rate constant (kOH) of approximately 1.97 × 10−11 cm3 molecule−1 s−1 at 300 K. The branching fraction analysis indicates a pronounced dominance of C-centered NH2 (Formula presented.) HOH radicals with a favorability of 77%, surpassing the N-centered (Formula presented.) HCH2OH (20%) and O-centered NH2CH2 (Formula presented.) (3%) radicals. Moreover, our investigation delves into the oxidation of the prominently favored carbon-centered NH2 (Formula presented.) HOH radical through its interaction with atmospheric oxygen molecules. Intriguingly, our findings reveal that formamide (NH2CHO) emerges as the predominant product in the NH2 (Formula presented.) HOH + 3O2 reaction, eclipsing alternative outcomes such as amino formic acid (NH2COOH) and formimidic acid (HN = C(H)-OH). At atmospheric conditions pertinent to the troposphere, the branching fraction value for the formation of formamide is about 99%, coupled with a rate constant of 5.5 × 10−12 cm3 molecule−1 s−1. Finally, we have scrutinized the detrimental impact of formamide on the atmosphere. Interaction of formamide with atmospheric hydroxyl radicals could give rise to the production of potentially perilous compounds such as HNCO. Further, unreacted (Formula presented.) HCH2OH radicals may initiate the formation of carcinogenic nitrosamines when reacting with trace N-oxides (namely, NO and NO2). This, in turn, escalates the environmental risk factors.
KW - aminomethanol
KW - DFT
KW - formamide
KW - photooxidalion
KW - rate constant
KW - transition state theory
UR - http://www.scopus.com/inward/record.url?scp=85195644955&partnerID=8YFLogxK
U2 - 10.3389/fchem.2024.1407355
DO - 10.3389/fchem.2024.1407355
M3 - Article
AN - SCOPUS:85195644955
SN - 2296-2646
VL - 12
JO - Frontiers in Chemistry
JF - Frontiers in Chemistry
M1 - 1407355
ER -