On the CH bond dipole moment in alkanes

The Thomas–Reiche–Kuhn sum rule, within the acceleration gauge for the transition dipole moment, is used to partition the total number of electrons in a molecule and to define atomic populations, which can be related to corresponding experimental estimates of atomic polar tensors from IR intensities. As a bond dipole moment can only be defined for diagonal atomic polar tensors, it is shown that the assumption of a C–H bond moment, transferable from molecule to molecule in the alkane series, is physically unreliable. From experimental IR intensities of methane we infer that, for the equilibrium geometry, µC–H =0.339 D, directed C−H+. Accordingly, it is argued that the theoretical bond dipole moments, estimated for the C–H bond in methane via localization procedures of SCF wave functions, are questionable, as they predict the opposite polarity. Finally, a resolution of the electric dipole moment into atomic contributions is suggested.