基组外推方法构建O（^3P）＋H2体系1^3A″的全维势能面

Full Dimensional Potential Energy Surface of 1^3A″ for O（^3P）＋H2 System by Basis Set Extrapolation Method

使用基于全活化空间自洽场(CASSCF)的多参考组态相互作用方法(MRCI+Q)和基组aug-cc-pV5Z构建了O(3P)+H2体系能量最低的13 A″和13 A′两个态的势能面,对13 A″态使用Varandas小组的外推方法,将基组aug-cc-pVQZ和aug-cc-pV5Z外推到完备基组极限(complete-basis-set limit).使用含时波包方法对新势能面进行动力学计算,并对比了只使用aug-cc-pV5Z基组时的速率常数,结果说明外推方法改进了势能面.

New accurate potential energy surfaces（PESs）for the lowest states（^3 A″and ^3 A′）of the O（^3P）＋H2reaction are proposed using an ab initio multireference configuration interaction method（MRCI）with Davidson correction and a large orbital basis set（aug-cc-pv5z）.The many-body expansion procedure is employed to describe the analytical PES function.The PES of the ^3 A″state is improved by using the extrapolation method in which aug-cc-pVQZ and aug-cc-pV5 Zbasis set extrapolation to the complete basis set limit（complete-basis-set limit）from the Varandas group.The topographical features of the new global PESs are presented and compared with previous surfaces.The quantum reaction scattering dynamics calculations are carried out over the collision energies range of 0.3-1.0eV on the new PESs.