Department of Mechanical Engineering, Indian Institute of Technology Bombay, Mumbai, India.
J Chem Phys. 2018 Feb 21;148(7):074305. doi: 10.1063/1.5008973.
A new global potential energy for the singlet spin state O system is reported using CASPT2/aug-cc-pVTZ ab initio calculations. The geometries for the six-dimensional surface are constructed using a novel point generation scheme that employs randomly generated configurations based on the beta distribution. The advantage of this scheme is apparent in the reduction of the number of required geometries for a reasonably accurate potential energy surface (PES) and the consequent decrease in the overall computational effort. The reported surface matches well with the recently published singlet surface by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. In addition to the O PES, the ground state N PES is also constructed using the point generation scheme and compared with the existing PES [Y. Paukku et al., J. Chem. Phys. 139, 044309 (2013)]. The singlet surface is constructed with the aim of studying high energy O-O collisions and predicting collision induced dissociation cross section to be used in simulating non-equilibrium aerothermodynamic flows.
使用 CASPT2/aug-cc-pVTZ 从头算计算，报道了 singlet spin state O 体系的新的全局势能。使用基于 beta 分布的随机生成构型的新的点生成方案构建了六维表面的几何形状。该方案的优点在于减少了合理准确的势能面（PES）所需的几何形状数量，从而降低了整体计算工作量。所报道的表面与 Paukku 等人最近发表的 singlet 表面[J. Chem. Phys. 147, 034301 (2017)]吻合得很好。除了 O PES 之外，还使用点生成方案构建了基态 N PES，并与现有 PES[Y. Paukku 等人，J. Chem. Phys. 139, 044309 (2013)]进行了比较。singlet 表面的构建目的是研究高能 O-O 碰撞，并预测用于模拟非平衡空气热力学流动的碰撞诱导离解截面。
