TY - JOUR
T1 - Combined DFT and NBO approach to analyze reactivity and stability of (CuS)n (n = 1–12) clusters
AU - Juárez-Sánchez, J. Octavio
AU - Galván, Donald H.
AU - Posada-Amarillas, Alvaro
N1 - Publisher Copyright:
© 2017 Elsevier B.V.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - Copper sulfide nanoparticles are attracting attention due to their interesting plasmonic properties, with potential applications in medicine and photocatalysis. In this work, copper sulfide clusters (CuS)n, n = 1–12, are theoretically studied through DFT and Natural Bond Orbital (NBO) analysis. Initial random structures were optimized using the DFT method to obtain ground state structures. CuS clusters adopt 3-D geometries from n = 4. Layered (n = 6, 8) and hollow (n = 4, 5, 7, 9, 10, 12) structures appear in this study, the latter with copper atoms forming hollow frameworks. Reactivity descriptors are calculated and electrophilicity index is correlated to electron affinity. Charge transfer occurs in general from copper to sulfur atoms, as shown by NBO analysis. For the closed-shell (CuS)6,8,10 clusters, stabilization energy shows that the dominant orbital interactions correspond to donor-acceptor orbitals σCuS→nCu∗,σCuS→σCuS∗,nS→σSS∗, respectively. Electrostatic potential maps reveal regions of large and low electron density surrounding S and Cu atoms, respectively.
AB - Copper sulfide nanoparticles are attracting attention due to their interesting plasmonic properties, with potential applications in medicine and photocatalysis. In this work, copper sulfide clusters (CuS)n, n = 1–12, are theoretically studied through DFT and Natural Bond Orbital (NBO) analysis. Initial random structures were optimized using the DFT method to obtain ground state structures. CuS clusters adopt 3-D geometries from n = 4. Layered (n = 6, 8) and hollow (n = 4, 5, 7, 9, 10, 12) structures appear in this study, the latter with copper atoms forming hollow frameworks. Reactivity descriptors are calculated and electrophilicity index is correlated to electron affinity. Charge transfer occurs in general from copper to sulfur atoms, as shown by NBO analysis. For the closed-shell (CuS)6,8,10 clusters, stabilization energy shows that the dominant orbital interactions correspond to donor-acceptor orbitals σCuS→nCu∗,σCuS→σCuS∗,nS→σSS∗, respectively. Electrostatic potential maps reveal regions of large and low electron density surrounding S and Cu atoms, respectively.
KW - Copper sulfide clusters
KW - DFT calculations
KW - NBO analysis
UR - http://www.scopus.com/inward/record.url?scp=85011627901&partnerID=8YFLogxK
U2 - 10.1016/j.comptc.2017.01.030
DO - 10.1016/j.comptc.2017.01.030
M3 - Artículo
SN - 2210-271X
VL - 1103
SP - 71
EP - 82
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -