 Solution

For a second-order response, $P_i^{(2)}({\omega }_3)={ϵ}_0{\sum }_{jk}{\chi }_{ijk}^{(2)}({\omega }_3;{\omega }_1,{\omega }_2)E_j({\omega }_1)E_k({\omega }_2)$, with the appropriate frequency conservation and negative-frequency convention for difference-frequency processes. Interchanging the two input field-frequency pairs gives intrinsic permutation symmetry of nonlinear susceptibility:For second-harmonic generation the input frequencies agree, so the last two Cartesian indices are symmetric and can be contracted into six input-pair labels. This reduces the unrestricted 27 Cartesian entries to at most 18 before crystal symmetries are imposed.

Crystal point-group transformations must leave the material tensor invariant and can force entries to vanish or become related. Under spatial inversion both electric field and polarization reverse, whereas the field product is even. A centrosymmetric bulk therefore has zero electric-dipole ${\chi }^{(2)}$. Surfaces and interfaces can break inversion symmetry, and higher-multipole processes are outside that simple prohibition.

Kleinman symmetry is a stronger approximate permutation symmetry used sufficiently far from resonances when dispersion can be neglected over the participating frequencies. It is not justified merely because two input frequencies are equal; resonant or appreciably dispersive media need the full frequency-dependent relations. These distinctions determine which polarization and propagation geometries have nonzero effective coupling, in addition to whether they satisfy phase matching.^[ref]