Badenes María P, Tucceri María E, Cobos Carlos J
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICET , Casilla de Correo 16, Sucursal 4, 1900 La Plata, Argentina.
J Phys Chem A. 2017 Jan 19;121(2):440-447. doi: 10.1021/acs.jpca.6b10427. Epub 2017 Jan 5.
The kinetics of the gas phase recombination reaction HO + HO + He → HOOOH + He has been studied between 200 and 600 K by using the SACM/CT model and the unimolecular rate theory. The molecular properties of HOOOH were derived at the CCSD(T)/aug-cc-pVTZ ab initio level of theory, while relevant potential energy features of the reaction were calculated at the CCSD(T)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVDZ level. The resulting high and low pressure limit rate coefficients are k = 3.55 × 10 (T/300) cm molecule s and k = [He] 1.55 × 10 (T/300) cm molecule s. The rate coefficients calculated over the 6 × 10 - 400 bar range are smaller at least in a factor of about 60 than the consensus value determined for the main reaction channel HO + HO → HO + O, indicating that the recombination pathway is irrelevant.
通过使用SACM/CT模型和单分子速率理论，在200至600 K之间研究了气相复合反应HO + HO + He → HOOOH + He的动力学。HOOOH的分子性质是在CCSD(T)/aug-cc-pVTZ从头算理论水平上推导出来的，而反应的相关势能特征是在CCSD(T)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVDZ水平上计算的。由此得到的高压和低压极限速率系数分别为k = 3.55 × 10 (T/300) cm³ molecule⁻¹ s⁻¹和k = [He] 1.55 × 10 (T/300) cm³ molecule⁻¹ s⁻¹。在6×10⁻⁴至400 bar范围内计算得到的速率系数至少比为主要反应通道HO + HO → HO₂ + O确定的共识值小约60倍，这表明复合途径是无关紧要的。
