Plane wave/pseudopotential implementation of excited state gradients in density functional linear response theory: a new route via implicit differentiation

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This work presents the formalism and implementation of excited state nuclear forces within density functional linear response theory (TDDFT) using a plane wave basis set. An implicit differentiation technique is developed for computing nonadiabatic coupling between Kohn-Sham molecular orbital wavefunctions as well as gradients of orbital energies which are then used to calculate excited state nuclear forces. The algorithm has been implemented in a plane wave/pseudopotential code taking into account only a reduced active subspace of molecular orbitals. It is demonstrated for the H₂ and N₂ molecules that the analytical gradients rapidly converge to the exact forces when the active subspace of molecular orbitals approaches completeness.