Kulkarni Anant D, Rai Dhurba, Bartolotti Libero J, Pathak Rajeev K
Department of Chemistry, University of Pune, Pune 411 007, India.
J Phys Chem A. 2006 Oct 26;110(42):11855-61. doi: 10.1021/jp0641536.
The present article comprises a theoretical study of structures and energetics of the lowest energy conformers of peroxyformic acid (PFA) and its hydrated variants, viz. PFA...(H2O)n (n = 1-4), at the molecular level. We have employed two different ab initio quantum chemical methods, viz. restricted Hartree-Fock (RHF) and the second-order Møller-Plesset (MP2) perturbation theory with the basis sets 6-31G(d,p) and 6-311++G(2d,2p). Modifications in the structure as well as vibrational frequencies of PFA brought about by successive addition of H2O molecules are also discussed. Cooperativity of hydrogen bonding in these clusters can be gauged through a detailed many body interaction energy analysis.
本文包含对过氧甲酸（PFA）及其水合变体，即PFA...(H2O)n（n = 1 - 4）最低能量构象异构体的结构和能量学的分子水平理论研究。我们采用了两种不同的从头算量子化学方法，即受限Hartree - Fock（RHF）和二阶Møller - Plesset（MP2）微扰理论，并使用了6 - 31G(d,p)和6 - 311++G(2d,2p)基组。还讨论了通过连续添加水分子对PFA的结构以及振动频率所带来的变化。通过详细的多体相互作用能分析，可以衡量这些团簇中氢键的协同作用。
