Hammett and Brown correlations in the structure and electronic properties of H2Si=SiHAr (Ar = p-C6H4X; X = NH2, OH,Me, H,F, Cl,CHO, COOH,CN, NO2) molecules |
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Authors: | Simin Samavat Reza Ghiasi Bita Mohtat |
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Institution: | 1. Department of Chemistry, Karaj Branch, Islamic Azad University, Karaj, Iran;2. Department of Chemistry, East Tehran Branch, Islamic Azad University, Tehran, Iran |
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Abstract: | Substituent effect on the structure and electronic properties of H2Si=SiHAr (Ar = p-C6H4X; X = NH2, OH, Me, H, F, Cl, CHO, COOH, CN, NO2) 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 H2Si and SiHAr fragments in HArSi=SiH2 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 (σp and σp+, respectively) are provided. Also, time-dependent density functional theory method (TD-DFT) is employed for the determination of the strongest absorption band values (λmax,el) of these molecules. This absorption band is attributed to the HOMO →LUMO transition. |
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Keywords: | disilenes energy decomposition analysis (EDA) spin isomers substituent effect time-dependent DFT (TD-DFT) |
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