Nonlinear optical susceptibility (${\chi }^{(2)}$)

Choose one driving electric field component and one responding electric polarization component. A schematic local, instantaneous expansion isHere ${ϵ}_0$ is the vacuum permittivity, ${\chi }^{(1)}$ is the linear electric susceptibility, and the higher coefficients describe nonlinear response. In SI, $P$ has units $\mathrm{C}{\mathrm{m}}^{-2}$, $E$ has units $\mathrm{V}{\mathrm{m}}^{-1}$, and ${\chi }^{(2)}$ has units $\mathrm{m}{\mathrm{V}}^{-1}$. The selected scalar coefficient depends on polarization of waves and crystal orientation; it is not a universal material number independent of geometry.

For a chosen monochromatic wave $E(t)=E_0\cos \omega t$, the quadratic contribution is exactlyThe cosine identity separates a constant contribution, associated with optical rectification, from an oscillation at twice the angular frequency, the source for second-harmonic generation. A term oscillating at $2\omega$ is a local driving source; efficient outgoing light additionally requires propagation and phase matching.

For a material with optical dispersion, the scalar instantaneous expansion is only a teaching model. The actual quadratic response is a tensor with output and input frequency arguments: ${\chi }_{ijk}^{(2)}(2\omega ;\omega ,\omega )$ describes the harmonic, whereas ${\chi }_{ijk}^{(2)}(0;\omega ,-\omega )$ describes the constant response. Their coefficients need not coincide. The cosine calculation establishes which frequencies are available, without assigning measured coefficients to any crystal.

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.