Armentrout P B
Department of Chemistry, University of Utah, 315 S 1400 E Rm 2020, Salt Lake City, Utah 84112, USA.
J Chem Phys. 2022 May 21;156(19):194301. doi: 10.1063/5.0091510.
The kinetic energy dependences of the reactions of Pt (D) with SO were studied using a guided ion beam tandem mass spectrometer and theory. The observed cationic products are PtO and PtSO, with small amounts of PtS, all formed in endothermic reactions. Modeling the kinetic energy dependent product cross sections allows determination of the product bond dissociation energies (BDEs): D(Pt-O) = 3.14 ± 0.11 eV, D(Pt-S) = 3.68 ± 0.31 eV, and D(Pt-SO) = 3.03 ± 0.12 eV. The oxide BDE agrees well with more precise literature values, whereas the latter two results are the first such measurements. Quantum mechanical calculations were performed for PtO, PtS, PtO , and PtSO at the B3LYP and coupled-cluster with single, double, and perturbative triple [CCSD(T)] levels of theory using the def2-XZVPPD (X = T, Q) and aug-cc-pVXZ (X = T, Q, 5) basis sets and complete basis set extrapolations. These theoretical BDEs agree well with the experimental values. After including empirical spin-orbit corrections, the product ground states are determined as PtO (Σ), PtS (Σ), PtO (Σ ), and PtSO (A'). Potential energy profiles including intermediates and transition states for each reaction were also calculated at the B3LYP/def2-TZVPPD level. Periodic trends in the thermochemistry of the group 9 metal chalcogenide cations are compared, and the formation of PtO from the Pt + SO reaction is compared with those from the Pt + O, CO, CO, and NO reactions.
使用导向离子束串联质谱仪和理论研究了Pt (D) 与SO反应的动能依赖性。观察到的阳离子产物是PtO和PtSO，还有少量的PtS，它们均在吸热反应中形成。对动能依赖性产物截面进行建模可以确定产物的键解离能 (BDE)：D(Pt-O) = 3.14 ± 0.11 eV，D(Pt-S) = 3.68 ± 0.31 eV，以及D(Pt-SO) = 3.03 ± 0.12 eV。氧化物的BDE与更精确的文献值吻合良好，而后两个结果是首次此类测量。使用def2-XZVPPD (X = T, Q) 和aug-cc-pVXZ (X = T, Q, 5) 基组并进行完全基组外推，在B3LYP和单、双、微扰三重耦合簇 [CCSD(T)] 理论水平上对PtO、PtS、PtO⁺ 和PtSO进行了量子力学计算。这些理论BDE与实验值吻合良好。纳入经验自旋轨道校正后，确定产物基态为PtO (Σ)、PtS (Σ)、PtO⁺ (Σ⁺) 和PtSO (A')。还在B3LYP/def2-TZVPPD水平上计算了每个反应包括中间体和过渡态的势能面。比较了第9族金属硫属化物阳离子热化学的周期性趋势，并将Pt + SO反应中PtO的形成与Pt + O、CO、CO₂ 和NO反应中的形成进行了比较。
