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Theoretical insight into the open‐shell singlet diradical character of single molecular solvated dielectron e 2 @C n F n ( n = 20, 28, 36, 50, 60, and 80)
Author(s) -
Wang YinFeng,
Huang Jiangen,
Li ZhiRu
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3625
Subject(s) - diradical , chemistry , singlet state , open shell , molecule , crystallography , atomic physics , physics , excited state , organic chemistry
Can there exist an open‐shell (OS) singlet diradical in the electronic ground state of the solvated dielectron? Here, we presented a comparison study by different cage‐shaped e 2 @C n F n ( n = 20, 28, 36, 50, 60, and 80) at unrestricted broken spin‐symmetry density functional theory. It is found that both the stability and the singlet diradical character of the molecule increase with increasing excess electron encapsulation space (size of the cage). For the e 2 @C n F n ( n = 50, 60, and 80), the electronic ground states have obvious special OS singlet diradical characters. Among these OS e 2 @C n F n ( n = 50, 60, and 80), the e 2 @C 50 F 50 with intermediate diradical character (0.658) is the most stable. The two semispheres in each highest occupied molecular orbital ( α and β ) of these diradicals suggest that the two excess electrons are simultaneously encapsulated inside the different regions of the cage, respectively, to form special broken s ‐type 3excess electron pair.