The Geometries and Stabilities of Neutral and Anionic Vanadium Doped Germanium Clusters VGen0/-( n = 9 - 13): Density Functional Theory Investigations

Abstract

The geometries, stabilities of VGen0/- (n = 9 - 13) clusters were systematically studied by the density functional theory (DFT) using the BP86 functional and LANL2DZ basis set. Several possible multiplicities of each cluster were tested to determine the most stable structure among the isomers. The average binding energy per atom, fragmentation energy, second order energy difference and HOMO-LUMO gaps were evaluated. The results indicated that the neutral and anionic clusters possess higher stability when n = 10 and 12. The vertical detachment energy (VDE) and adiabatic detachment energy (ADE) were also calculated for anionic cluster to investigate their stabilities. Among neutral clusters, VGe10 had both the highest vertical ionization potential (VIP) and chemical hardness.
 Keywords
 BP86/LANL2DZ, binding energy, VGen0/- clusters, structure of clusters
 References
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The Geometries, Stabilities and Electronic Property of Cationic Vanadium Doped Germanium Cluster GenV+ (n=9-13) from Density Functional Theory

“…Qua tìm hiểu về các nghiên cứu trước, chúng tôi thấy rằng chưa có một công trình nào khảo sát độ bền và cấu trúc của GenV (n = 10 -13) ở dạng cation. Vì vậy trong bài báo này, chúng tôi sẽ tiến hành nghiên cứu cấu trúc và độ bền của cluster Germanium pha tạp Vanadium dạng cation GenV + (n = 9-13) và so sánh với dạng trung hòa và dạng anion GenV 0/-(n=9-13) ở nghiên cứu trước [21] bằng phương pháp phiếm hàm mật độ.…”

“…Để tìm kiếm tất cả các đồng phân cation có thể có của mỗi cluster, chúng tôi đã dùng cấu trúc từ các cluster trung hòa và anion đã tìm kiếm trước đây [21] và tối ưu hóa ở những độ bội khác nhau. Các đồng phân anion, trung hòa và cation của cluster GenV -/0/+ được kí hiệu là tx-z, trong đó t là số nguyên tử Ge, t = 9 -13; x = n nếu cluster là trung hòa, x = c nếu cluster là cation (+), x = a nếu cluster là anion (-), z là số tự nhiên bắt đầu từ 1 đến 4 được sắp xếp tăng dần theo chiều tăng của năng lượng tương đối.…”

Atomic structures and growth of monoanion germanium-vanadium glusters VGe-=SUB=-n-=/SUB=--=SUP=---=/SUP=- (n=5-19): analysis based on the Wade-Mingos rule

“…The atomic structure and electronic properties of some anionic [51][52][53] and neutral [54] vanadium-germanium clusters have been studied earlier. However, each of the works has a number of significant features that do not allow us to assert the full adequacy of the results presented there.…”

“…In addition, the LANL2DZ basis is a valence basis, not a full-electron basis, which also does not include diffuse functions [55], which can also lead to inaccurate results in the calculation of anionic systems. The authors [53] give in their work the photoelectronic spectra of the VGe − n clusters (n = 3−12) and the results of optimization calculations of their atomic structure, but do not give the results of the calculated electron spectra of each isomer and, accordingly, cannot compare them with experimental spectra. Therefore, the results of calculations of atomic structures presented in [53] have not been confirmed experimentally.…”

“…The authors [53] give in their work the photoelectronic spectra of the VGe − n clusters (n = 3−12) and the results of optimization calculations of their atomic structure, but do not give the results of the calculated electron spectra of each isomer and, accordingly, cannot compare them with experimental spectra. Therefore, the results of calculations of atomic structures presented in [53] have not been confirmed experimentally. The same drawback can be noted in the work [54], which presents the results of the calculation of the atomic structures of neutral germaniumvanadium clusters.…”