Do computed crystal structures of nonpolar molecules depend on the electrostatic interactions? The case of tetracene.
We present a strategy for comparing the global properties of competing potential models. By systematically sampling the potential energy surface of crystalline tetracene, we assess how the number, energy and structure of its minima are modified by switching on (or off) the Coulombic interactions. The increased complexity of the Coulombic potential leads to a more "rugged" potential energy surface with a larger number of minima, but the effect is not large. In fact, we find a subset of minima stable only in presence of the Coulombic interactions, a smaller subset stable only in their absence, and a large majority stable in both cases. Among these, there is a very good, but not perfect, correlation between the energies and the structures computed with and without the electrostatic interactions. Although electrostatic interactions play a role even in a rigid nonpolar molecule such as tetracene, they are not as crucial as often believed, because altering the electrostatic model (or switching it off completely) leads, in most cases, to equivalent results.
Della Valle
Raffaele Guido
RG
Dipartimento di Chimica Fisica e Inorganica and INSTM-UdR Bologna, Università di Bologna, Viale Risorgimento 4, I-40136 Bologna, Italy. valle@aronte.fci.unibo.it
Venuti
Elisabetta
E
Brillante
Aldo
A
Girlando
Alberto
A