TY - JOUR
T1 - From Molecules to Solids
T2 - A vdW-DF-C09 Case Study of the Mercury Dihalides
AU - Cooper, Valentino R.
AU - Krogel, Jaron T.
AU - Donald, Kelling J.
N1 - Publisher Copyright:
©
PY - 2021/5/13
Y1 - 2021/5/13
N2 - The mercury dihalides show a remarkable diversity in the structural preferences in their minimum energy structure types, spanning molecular to strongly bound ionic solids. A challenge in the development of density functional methods for extended systems is to arrive at strategies that serve equally well such a broad range of bonding modes or structural preferences. The chemical bonding and the stabilities of mercury dihalides and the general utility and reliability of the van der Waals density functional with C09 exchange (vdW-DF-C09) in predicting or describing the energetics and structural preferences in these metal dihalides is examined. We show that, in contrast with the uncorrected generalized gradient approximation of the Perdew-Burke-Erzenhoff (PBE) exchange-correlation functional, qualitative and quantitative patterns in the bonding of the mercury dihalide solids are well reproduced with vdW-DF-C09 for the full series of HgX2 systems for X = F, Cl, Br, and I. The possible existence of a low-temperature cotunnite polymorph for HgF2 and PbF2 is posited.
AB - The mercury dihalides show a remarkable diversity in the structural preferences in their minimum energy structure types, spanning molecular to strongly bound ionic solids. A challenge in the development of density functional methods for extended systems is to arrive at strategies that serve equally well such a broad range of bonding modes or structural preferences. The chemical bonding and the stabilities of mercury dihalides and the general utility and reliability of the van der Waals density functional with C09 exchange (vdW-DF-C09) in predicting or describing the energetics and structural preferences in these metal dihalides is examined. We show that, in contrast with the uncorrected generalized gradient approximation of the Perdew-Burke-Erzenhoff (PBE) exchange-correlation functional, qualitative and quantitative patterns in the bonding of the mercury dihalide solids are well reproduced with vdW-DF-C09 for the full series of HgX2 systems for X = F, Cl, Br, and I. The possible existence of a low-temperature cotunnite polymorph for HgF2 and PbF2 is posited.
UR - http://www.scopus.com/inward/record.url?scp=85103770002&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.0c10847
DO - 10.1021/acs.jpca.0c10847
M3 - Article
C2 - 33724850
AN - SCOPUS:85103770002
SN - 1089-5639
VL - 125
SP - 3978
EP - 3985
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 18
ER -