The aim of this study is to calculate the unimolecular rate coefficients for the unimolecular decomposition reaction of the industrially important molecule, SF₆. The energies of stationary-points involved in the title reaction are calculated by the combination W1 method. Two main reaction paths are considered: SF₆ → SF₅ + F (R1) and SF₆ → SF₄ + F₂ (R2). Having information on energies and molecular properties of reactants and transition-states, RRKM statistical rate theory is used to compute the rate coefficients as a function of temperature and pressure. For the bond dissociation process R1, special version of RRKM theory, i. e., Variable reaction coordinate-transition state theory (VRC-TST) is employed. Although the reaction R1 is the dominant process over a wide range of pressure and temperature, but the reaction R2 could be significant at high temperatures. The following Arrhenius expressions are obtained for high-pressure limiting rate constants of reaction paths R1 and R2:

k_∞,1 = 5.71 × 10¹⁶ s⁻¹ exp (−429.8 kJ mol⁻¹ /RT)

k_∞,2 = 2.14 × 10¹⁶ s⁻¹ exp (−590.6 kJ mol⁻¹ /RT).

这项研究的目的是计算工业上重要分子SF ₆的单分子分解反应的单分子速率系数。标题反应中涉及的固定点的能量是通过组合W1方法计算的。考虑了两个主要反应路径：SF ₆  →SF ₅  + F（R1）和SF ₆  →SF ₄  + F ₂（R2）。具有关于反应物的能量和分子性质以及过渡态的信息，RRKM统计速率理论用于计算作为温度和压力的函数的速率系数。对于键解离过程R1，使用特殊形式的RRKM理论，即可变反应坐标-过渡态理论（VRC-TST）。尽管反应R1是在很大的压力和温度范围内的主要过程，但反应R2在高温下可能很重要。对于反应路径R1和R2的高压极限速率常数，获得以下Arrhenius表达式：

ķ _∞，1  = 5.71×10 ¹⁶ 小号^-1 EXP（-429.8千焦摩尔^-1 / RT）

ķ _∞，2  = 2.14×10 ¹⁶ 小号^-1 EXP（-590.6千焦摩尔^-1 / RT）。