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A theoretical study on the stability difference of the borane B n H n 2 − and carborane C 2 B n −2 H n (5 ≤ n ≤ 7) clusters
Author(s) -
Liao Rongbao,
Chai Lanlan,
Zhu Yun
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24834
Subject(s) - borane , carborane , molecular orbital , chemistry , cluster (spacecraft) , ring (chemistry) , icosahedral symmetry , homo/lumo , crystallography , computational chemistry , binding energy , atomic orbital , atomic physics , stereochemistry , physics , molecule , organic chemistry , nuclear physics , computer science , programming language , catalysis , electron
In order to study the electronic structure and structural stability of boraneB n H n 2 −and carborane C 2 B n −2 H n (5 ≤ n ≤ 7) clusters, especially the stability difference between the boraneB 5 H 5 2 −and carborane C 2 B 3 H 5 . The frontier orbital energy levels of the boraneB n H n 2 −and carborane C 2 B n −2 H n (5 ≤ n ≤ 7) clusters are calculated at CCSD(T)/aug‐cc‐pVXZ//B3LYP/def2‐TZVPP level. The results are further analyzed by qualitative frontier orbital method based on the cap–ring interaction. The results reveal that: (1) the larger E gap (HOMO‐LUMO energy gap) of carborane C 2 B n −2 H n (5 ≤ n ≤ 7) clusters than boraneB n H n 2 −(5 ≤ n ≤ 7) clusters originates from the more effective cap–ring orbital overlap of carborane C 2 B n −2 H n (5 ≤ n ≤ 7) clusters than that of boraneB n H n 2 −(5 ≤ n ≤ 7) clusters; (2) the smallest E gap of the boraneB 5 H 5 2 −results from the highest energy level of the ring symmetry‐adapted linear combination orbital ofB 5 H 5 2 −cluster; and (3) the largest E gap of the carborane C 2 B 3 H 5 is induced by the most effective cap–ring orbital interaction of C 2 B 3 H 5 cluster. © 2014 Wiley Periodicals, Inc.