Bulk electric-dipole selection rule (${\chi }^{(2)}=0$)

Suppose a homogeneous bulk material is unchanged when all spatial coordinates are reversed. Both electric polarization and electric field reverse under this inversion, so a local electric dipole response must obey $P(-E)=-P(E)$. Substituting the nonlinear optical susceptibility expansion givesFor every sufficiently small $E$, all even coefficients vanish. In the full tensor relation, two reversed input electric fields leave their product unchanged while the output electric polarization changes sign, forcing every bulk electric-dipole component of ${\chi }^{(2)}$ to vanish.

The qualification matters: the argument assumes inversion symmetry, a local bulk electric dipole response, and no applied bias that breaks that symmetry. A surface breaks bulk inversion symmetry; spatially varying or magnetic responses also lie outside this local electric-dipole model. Thus detecting second-harmonic generation at a surface or through a weaker magnetic contribution does not contradict the bulk selection rule. Conversely, absence of inversion symmetry permits some quadratic components but does not guarantee a nonzero component in every beam geometry.