Alessandro Erba

A computational procedure is developed for the efficient calculation of derivatives of integrals over non-separable Gaussian-type basis functions, used for the evaluation of gradients of the total energy in quantum-mechanical simulations. The approach, based on symbolic computation with computer algebra systems and automated generation of optimized subroutines, takes full advantage of sparsity and is here applied to first energy derivatives with respect to nuclear displacements and lattice parameters of molecules and materials. The implementation in the Crystal code is presented, and the considerably improved computational efficiency over the previous implementation is illustrated. For this purpose, three different tasks involving the use of analytical forces are considered: (i) geometry optimization; (ii) harmonic frequency calculation; and (iii) elastic tensor calculation. Three test case materials are selected as representatives of different classes: (i) a metallic 2D model of the Cu(111) surface; (ii) a wide-gap semiconductor ZnO crystal, with a wurtzite-type structure; and (iii) a porous metal-organic crystal, namely the ZIF-8 zinc-imidazolate framework. Finally, it is argued that the present symbolic approach is particularly amenable to generalizations, and its potential application to other derivatives is sketched.