[en] We show that electrodynamic dipolar interactions, responsible for long-range fluctuations in matter, play a significant role in the stability of molecular crystals. Density functional theory calculations with van der Waals interactions determined from a semilocal ``atom-in-a-molecule'' model result in a large overestimation of the dielectric constants and sublimation enthalpies for polyacene crystals from naphthalene to pentacene, whereas an accurate treatment of nonlocal electrodynamic response leads to an agreement with the measured values for both quantities. Our findings suggest that collective response effects play a substantial role not only for optical excitations, but also for cohesive properties of noncovalently bound molecular crystals. DOI: 10.1103/PhysRevB.87.060104
Disciplines :
Physique
Auteur, co-auteur :
Schatschneider, Bohdan; The Pennsylvania State University, Fayette, The Eberly Campus, Lemont Furnace, Pennsylvania 15456, USA
Liang, Jian-Jie; Accelrys Inc., 10188 Telesis Court, Suite 100, San Diego, California 92121, USA
Reilly, Anthony M.; Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Marom, Noa; Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, Texas 78712, USA
Zhang, Guo-Xu; Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
