Correlation between Pseudo Jahn–Teller Effect Parameters, Hardness, and LP-LP Repulsion on Structural and Configurational Behaviors of Hydrazine, Diphosphane, and Diarasane

Pleiades Publishing Ltd - Tập 95 - Trang 604-612 - 2021
Abdolkhalegh Mohammadizadeh1, Reza Fazaeli2
1Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran
2Department of Chemistry, South Tehran Branch, Islamic Azad University, Tehran, Iran

Tóm tắt

It has been shown that high-symmetry forms of any molecule undergo structural distortions due to the pseudo Jahn–Teller effect (PJTE). The cis-bent ( $${{C}_{{2{v}}}}$$ ) and flat (D2h) configuration of hydrazine (1), diphosphane (2), and diarsane (3) were optimized at the CAM-B3LYP, B3LYP, and LC-ωPBE methods with the 6-311+G** basis set. Studies on the relationship between PJT’s stabilization energies, structural and hardness factors of compounds 1–3 have been investigated. The energy difference between the reference values (Δ) in the flat (D2h) geometries reduces from composition 1 to 3 (3.93, 1.96, and 0.93 eV). The calculated Δ[η( $${{C}_{{2{v}}}}$$ ) – η(D2h)] parameter increases from compound 1 to 3. It was found that D2h is more instable $${{C}_{{2{v}}}}$$ configuration, Due to the repulsion of strong lone pair–lone pair. PJT stability energy rises from compound 1 to 3, which shows a higher stability of compositions 1–3 (0.2, 1.42, and 2.05 eV, respectively).

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