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Hammett and Brown correlations in the structure and electronic properties of H 2 Si=SiHAr (Ar = p ‐C 6 H 4 X; X = NH 2 , OH, Me, H, F, Cl, CHO, COOH, CN, NO 2 ) molecules
Author(s) -
Samavat Simin,
Ghiasi Reza,
Mohtat Bita
Publication year - 2020
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.202000037
Subject(s) - chemistry , homo/lumo , substituent , molecule , density functional theory , singlet state , crystallography , band gap , electronic structure , absorption spectroscopy , computational chemistry , stereochemistry , atomic physics , excited state , organic chemistry , physics , quantum mechanics
Substituent effect on the structure and electronic properties of H 2 Si=SiHAr (Ar = p ‐C 6 H 4 X; X = NH 2 , OH, Me, H, F, Cl, CHO, COOH, CN, NO 2 ) molecules are studied at the CAM‐B3LYP/6‐311G(d,p) level of theory. Energy decomposition analysis (EDA) is used as a useful tool for illustrating the interaction between H 2 Si and SiHAr fragments in HArSi=SiH 2 molecules. Energetic analysis reveals that the singlet state of the fragments is more stable than triplet state. Also, interactions are stronger in the presence of electron‐withdrawing groups (EWGs) in comparison to electron donating groups (EDGs). EDG and EDG effects are investigated on the stability of fragments, frontier orbital energy, distortion, HOMO–LUMO gap, electron‐donating ( ω − ) and electron‐accepting ( ω + ) powers of the studied molecules. Then, the correlations between these calculated parameters with the Hammett and Brown constants ( σ p and σ p + , respectively) are provided. Also, time‐dependent density functional theory method (TD‐DFT) is employed for the determination of the strongest absorption band values ( λ max,el ) of these molecules. This absorption band is attributed to the HOMO →LUMO transition.