Control of ionic properties of N-nitrosodimethylamine through hydrogen substitution by fluorine atoms

Abstract

In this paper the effect of hydrogen substitution by fluorine on the dipole moment and static isotropic polarizabilities of N-nitrosodimethylamine has been studied through ab initio (MP2) and DFT (B3LYP) calculations with the cc-pVTZ basis set. It has been found that most of the 40 different substitution patterns lead to a decrease of dipole moment upon fluorine substitution, and in some cases the decrease is quite substantial (for instance, from about 4.3 to 0.4 D at MP2 level). Three types of substitution cause an increase in the dipole moment, but of at most ~0.5 and 0.8 D at the B3LYP and MP2 levels, respectively. The changes in the dipole moment are largely dependent on the number and location of the fluorine atoms, but some positions are more important than others, especially as up to three fluorine atoms are used. On the other hand, the changes in the polarizabilities are of minor importance.