Rav Kamal Kant, Sonika Kumari, Sonker Ekta, Rao Pradeep Kumar
Department of Chemistry, Deen Dayal Upadhyaya Gorakhpur University, Gorakhpur, 273009, India.
J Mol Model. 2025 May 30;31(6):177. doi: 10.1007/s00894-025-06400-0.
1,1,2,2- tetrafluoroethene (TFE) is a class of per fluoroalkenes. The reaction of TFE with ozone is significant in the atmospheric oxidation of per fluoroalkenes. Kinetics of TFE + O reaction in absence of as well as in presence of single water molecule act as catalyst has been analysed in gas phase as well as in solvent phase. The impact of water solvated environment is demonstrated to be significant to the extent that even single water molecules can function as catalysts in the ozonolysis of titled molecule. The computations related to the coordination of a single water molecule illustrate distinctly the notable decrease in the energy barrier and the substantial lowering of the activation energy. The investigation revealed that the mechanism of this reaction, which is facilitated by water as catalyst presents greater kinetic benefits compared to its non-catalytic counterpart. Calculated rate constant for water catalyzed and non catalyzed ozonolysis of titled molecule were estimated to be 1.0 × 10 cmmolecule s and 3.0 × 10 cmmolecule srespectively. The atmospheric lifetimes, radiative forcing and global warming potential (GWP) have been determined as well.
All electronic structure calculations have been done employing Gaussian 09 software package. Geometry optimizations and frequency calculations have been performed using DFT/M06-2X/6-311 + G(d,p) method. The energies were further refined and potential energy were constructed at CCSD(T)/6-311 + G(d,p) level.
1,1,2,2 - 四氟乙烯（TFE）是一类全氟烯烃。TFE与臭氧的反应在全氟烯烃的大气氧化过程中具有重要意义。已在气相和溶剂相中分析了在不存在以及存在单个水分子作为催化剂的情况下TFE + O反应的动力学。结果表明，水合环境的影响非常显著，以至于即使单个水分子也能在标题分子的臭氧分解反应中起到催化作用。与单个水分子配位相关的计算清楚地表明了能垒的显著降低和活化能的大幅下降。研究发现，与无催化反应相比，以水为催化剂促进的该反应机制具有更大的动力学优势。经计算，标题分子在水催化和无催化臭氧分解反应中的速率常数分别估计为1.0×10⁻¹⁰cm³·molecule⁻¹·s⁻¹和3.0×10⁻¹⁵cm³·molecule⁻¹·s⁻¹。还确定了大气寿命、辐射强迫和全球变暖潜能值（GWP）。
所有电子结构计算均使用高斯09软件包完成。采用DFT/M06 - 2X/6 - 311 + G(d,p)方法进行几何结构优化和频率计算。能量进一步细化，并在CCSD(T)/6 - 311 + G(d,p)水平构建势能。
