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Electronic structure and thermochemical properties of silicon‐doped lithium clusters Li n Si 0/+ , n = 1–8: New insights on their stability
Author(s) -
Tai Truong Ba,
Nguyen Minh Tho
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.22911
Subject(s) - silicon , cluster (spacecraft) , chemistry , dissociation (chemistry) , ionization energy , binding energy , doping , lithium (medication) , crystallography , atomic physics , basis set , cationic polymerization , adiabatic process , density functional theory , ionization , ion , computational chemistry , physics , thermodynamics , condensed matter physics , medicine , organic chemistry , endocrinology , computer science , programming language
A theoretical investigation on small silicon‐doped lithium clusters Li n Si with n = 1–8, in both neutral and cationic states is performed using the high accuracy CCSD(T)/complete basis set (CBS) method. Location of the global minima is carried out using a stochastic search method and the growth pattern of the clusters emerges as follows: (i) the species Li n Si with n ≤ 6 are formed by directly binding one Li to a Si of the smaller cluster Li n −1 Si, (ii) the structures tend to have an as high as possible symmetry and to maximize the coordination number of silicon. The first three‐dimensional global minimum is found for Li 4 Si, and (iii) for Li 7 Si and Li 8 Si, the global minima are formed by capping Li atoms on triangular faces of Li 6 Si ( O h ). A maximum coordination number of silicon is found to be 6 for the global minima, and structures with higher coordination of silicon exist but are less stable. Heats of formation at 0 K (Δ f H 0 ) and 298 K (Δ f H 298 ), average binding energies ( E b ), adiabatic (AIE) and vertical (VIE) ionization energies, dissociation energies ( D e ), and second‐order difference in total energy (Δ 2 E ) of the clusters in both neutral and cationic states are calculated from the CCSD(T)/CBS energies and used to evaluate the relative stability of clusters. The species Li 4 Si, Li 6 Si, and Li 5 Si + are the more stable systems with large HOMO–LUMO gaps, E b , and Δ 2 E . Their enhanced stability can be rationalized using a modified phenomenological shell model, which includes the effects of additional factors such as geometrical symmetry and coordination number of the dopant. The new model is subsequently applied with consistency to other impure clusters Li n X with X = B, Al, C, Si, Ge, and Sn. © 2012 Wiley Periodicals, Inc.