Groupe de Chimie Théorique et Réactivité IPREM-ECP, Université de Pau et des Pays de l'Adour, Pau F-64000, France.
J Chem Phys. 2018 Feb 14;148(6):064303. doi: 10.1063/1.5005989.
One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm relative to trans zero point energy.
已经在 CCSD(T)-F12a/aug-cc-pVTZ 水平上生成了一个针对 cis 和 trans 构象体的、完整的单维价坐标 HCOOH 基态位能面，精度高达 6000 cm 相对 trans 零点能。使用海德堡多组态含时密度泛函方法和 TANA 程序生成的价坐标动能的精确表达式，使用改进的弛豫方法，计算并分配了 trans- 和 cis-HCOOH 的基本振动模式及其一组本征函数，分别完整到约 3120 和 2660 cm。trans 基本跃迁频率的计算结果与实验值相差在 5 cm 以内。提出了一些重新分配的建议。我们的结果表明，在 3640 cm 相对 trans 零点能的范围内，振动本征函数没有 cis-trans 离域效应。
