Third-order energy derivative corrections to the Kohn–Sham orbital hardness tensor

The third term in the Taylor expansion of the total energy functional around the number of electrons N is evaluated as the second-order derivative of orbital Kohn–Sham energies with respect to orbital occupancy. Present approach is an extension of an efficient algorithm to compute densityfunctional based orbital reactivity indices. Various energy derivatives used to approximate orbital reactivity indices are defined within the space spanned by the orbital occupation numbers and the Kohn– Sham one-electron energies. The third-order energy functional derivative has to be considered for singular hardness tensor ([n]). On the contrary, this term has negligible influence on the reactivity index values for atomic or molecular systems with positively defined hardness tensors. In this context, stability of a system in equilibrium state estimated through the eigenvalues of ([n]). is discussed. Numerical illustration of the Kohn–Sham energy functional derivatives in orbital resolution up to the third order is shown for benchmark molecules such as H2O, H2S, and OH–.