physical chemistry - How does a lone pair of a central atom affect the dipole moment?

Dipole moment is the degree of polarity, i.e. the seperation of positive and negative charges. But I am not getting the intuition why and how lone pairs affect the polarity and dipole moment. I cannot connect the separation of positive and negative charges definition with lone pair.

Answer

How does lone pair of a central atom affect the dipole moment?

There is no single answer to your question, let me explain. Unlike a typical covalent bond where the electrons are shared between two nuclei and the electron density is spread out over the entire bond, in a lone pair the electrons are not shared and the electron density is more localized around the atom that has the lone pair of electrons. This increased electron density could lead to a more significant contribution from the lone pair electrons to the molecular dipole moment than from electrons spread out more diffusely in a covalent bond. Next we must understand the directionality of the lone pair of electrons. Consider the two molecules pictured below, ammonia and phosphine. The molecules appear to be very similar, they are in the same column in the Periodic Table.

However in ammonia the $\ce{H-N-H}$ angle is around 107 degrees and the molecule is roughly $\ce{sp^3}$ hybridized, the lone pair and the 3 $\ce{N-H}$ bonds roughly pointing towards the corners of a tetrahedron. You can see that in this case (as shown by the arrows, the "arrowhead" end representing the negative end of a dipole), the lone pair on nitrogen will make a contribution to the molecular dipole moment. Next, let's examine phosphine. The $\ce{H-P-H}$ angle is around 90 degrees and the molecule can be viewed as being unhybridized, the lone pair is an $\ce{s}$ orbital and the 3 $\ce{P-H}$ bonds are constructed from phosphorous $\ce{p}$ orbitals. You can see that in this case, the lone pair on phosphorous, due to its spherical symmetry will not make a contribution to the overall molecular dipole moment.

So in summary, a lone pair of electrons can make a significant contribution to the magnitude of a molecular dipole moment due to the fact that they are more localized than bonding electrons and consequently there is a high electron density. But, the directionality (or lack thereof) of the lone pair must also be assessed, since a lack of directionality may preclude it from making a significant contribution to the overall molecular dipole moment.