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Effect of terminal groups on the electronic structure of hyperbranched polyacetylene
Author(s) -
Fomina Lioudmila,
Ponce Patricia,
Guadarrama Patricia,
Fomine Serguei
Publication year - 1999
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/(sici)1521-3919(19990901)8:5<403::aid-mats403>3.0.co;2-o
Subject(s) - steric effects , polyacetylene , dendrimer , electron affinity (data page) , electronic structure , chemistry , ionization energy , molecule , computational chemistry , electronic effect , electron , terminal (telecommunication) , lone pair , proton affinity , crystallography , chemical physics , stereochemistry , ionization , polymer chemistry , organic chemistry , physics , polymer , quantum mechanics , ion , telecommunications , computer science , protonation
Quantum mechanics calculations at B3LYP/6‐31G (d)//HF/3‐21G (d) level of the theory were carried out on second generation dendritic polyacetylenic oligomers bearing different terminal groups to clarify the impact of their nature on the electronic structure of hyperbranched polyacetylene. It was found that steric and electronic factors affect the electronic properties of the studied dendrimers. While the steric hindrances independently of the nature of a terminal group tend to increase band gap and ionisation potential and decrease electron affinity, the interaction of lone electron pairs and π‐electrons of the terminal groups with the rest of the molecule produces specific changes in the electronic structure of each particular group. A general feature of the studied dendrimers is that upon ionisation or addition of an electron to the dendrimer the molecules become more planar.