Decomposition of Pyruvic Acid on the Ground-State Potential Energy Surface
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- 作者：Gabriel da Silva
- 刊名：Journal of Physical Chemistry A
- 出版年：2016
- 出版时间：January 21, 2016
- 年：2016
- 卷：120
- 期：2
- 页码：276-283
- 全文大小：451K
- ISSN：1520-5215
文摘
A potential energy surface is reported for isomerization and decomposition of gas-phase pyruvic acid (CH3C(O)C(O)OH) in its ground electronic state. Consistent with previous works, the lowest energy pathway for pyruvic acid decomposition is identified as decarboxylation to produce hydroxymethylcarbene (CH3COH), with overall barrier of 43 kcal mol–1. This study discovers that pyruvic acid can also isomerize to the α-lactone form with a barrier of only 36 kcal mol–1, from which CO elimination can occur at 49 kcal mol–1 above pyruvic acid. An additional novel channel is identified for the tautomerisation of pyruvic acid to the enol form, via a double H-shift mechanism. The barrier for this process is 51 kcal mol–1, which is around 20 kcal mol–1 lower than the barrier for conventional keto–enol tautomerization via a 1,3-H shift transition state. Rate coefficients are calculated for pyruvic acid decomposition through RRKM theory/master equation simulations at 800–2000 K and 1 atm, showing good agreement with the available experimental data. The dissociation of vibrationally excited pyruvic acid produced through photoexcitation and subsequent internal conversion to the ground state is also modeled under tropospheric conditions and is seen to produce appreciable quantities of CO (～1–4%) in addition to CH3COH via the dominant CO2 loss channel.