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• W4387665904 abstract "Abstract Detailed chemical kinetic mechanisms for the synthesis of complex organic molecules in the interstellar medium are at an early stage of developement. That such synthesis must take place is well‐known from chemical analysis of sampled asteroids. As molecular complexity increases the number of possible structural isomers also increases with the consequence that the nascent species may adopt a different spatial arrangement, to the lowest energy one. As part of a program of investigations of the hydrogen atom transfer reaction or tautomerization of imidic acid–amide species H‐O=C‐N‐ O=C‐N‐H we have studied the kinetics for a number of nucleobases, namely cytosine, thymine and uracil where a cyclic form of tautomerism (lactim–lactam) is encountered. Together with a fourth, 5‐aza‐uracil (1,3,5‐triazine‐2,4(1 H ,3 H )‐dione), we report on the rates of reaction at low temperatures 50–200 K for both the direct unimolecular process and the similar transformation mediated by an additional water molecule. We show that these tautomerization reactions can be categorized into three classes, and highlight the importance of quantum mechanical tunneling on the rate constants at these low temperatures. We further present some thermochemistry data, such as formation enthalpies, entropies, isobaric heat capacities and enthalpy functions." @default.
• W4387665904 created "2023-10-17" @default.
• W4387665904 creator A5057838991 @default.
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• W4387665904 date "2023-10-16" @default.
• W4387665904 modified "2023-10-17" @default.
• W4387665904 title "Kinetics of direct and water‐mediated tautomerization reactions of nucleobases at low temperatures ⩽200 K" @default.
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• W4387665904 doi "https://doi.org/10.1002/kin.21696" @default.
• W4387665904 hasPublicationYear "2023" @default.
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