Periodic local Møller-Plesset second order perturbation theory method applied to molecular crystals: study of solid NH3 and CO2 using extended basis sets.
We have calculated the equilibrium geometry, formation energy, and bulk modulus of two molecular bulk crystals, NH(3) and CO(2), at the periodic post-Hartree-Fock correlated level. The dependence of the results on the basis set has been analyzed, by employing basis sets up to aug-cc-pVQZ quality. In the calculations, we used the periodic local Møller-Plesset second order perturbation theory (LMP2), implemented in the CRYSCOR program. Multipolar expansion techniques, as well as density fitting, are employed in this code to reduce the number of and to factorize the required electron repulsion integrals; as a consequence of that, the computational cost for the correlation part of the calculations is comparable to that of the Hartree-Fock. Auxiliary calculations performed on molecular dimers are also reported to verify the accuracy of the LMP2 approach and of the basis sets used. Furthermore, the effect of spin-component scaling has been investigated for the two crystals. One intention of the present paper is also to lay out and specify the computational setup, which is generally applicable for accurate CRYSCOR calculations on molecular crystals.
Maschio
Lorenzo
L
Dipartimento di Chimica IFM and Centre of Excellence NIS (Nanostructured Interfaces and Surfaces), Università di Torino, via Giuria 5, I-10125 Torino, Italy. lorenzo.maschio@unito.it
Usvyat
Denis
D
Schütz
Martin
M
Civalleri
Bartolomeo
B