Polarization and bonding of the intrinsic characteristic contours of hydrogen and fluorine atoms of forming a hydrogen fluoride molecule based on an ab initio study

摘要

The spatial changing feature of the shapes and sizes of the system consisted of one hydrogen atom and one fluorine atom of forming a hydrogen fluoride molecule is investigated.We give formalism of the potential acting on an electron in a molecule and derive its concrete expression in Hartree-Fock self-consistent molecular orbital theory including configuration interaction.The program of calculating the potential acting on an electron in a molecule is programmed and compiled in the framework of the MELD program package.We formulate briefly the approach of the molecular intrinsic characteristic contour (MICC) which is defined in terms of the classical turning points of electronic motion.The MICC for a molecular system is intrinsic and can be calculated by means of an ab initio CI method.Then,the polarization and bonding features of the intrinsic characteristic contours of hydrogen and fluorine atoms forming a hydrogen fluoride molecule are presented and discussed from ab initio calculations.Furthermore,electron density distribution as an added dimension has been demonstrated on the changing MICC and thus the vivid polarization and bonding features for a chemical process have been shown.It seems that at the early stage (internuclear distance Ind = 5.0-20.0 a.u.) the fluorine atom gives more enthusiastic with the sensitive and expanded polarization to welcome coupling with the hydrogen atom while the latter has little response even "shy" with shrinking a bit its size at the beginning of putting the two atoms into a system and it is only around the critical point,the contact point (Ind=4.73 a.u.),that both of them stretch their hands and arms to meet and then fuse together.