Estimating structure, stability, and electronic properties on halogenated derivatives of 2-germabicyclo[1.1.1.]pentane-2-ylidenes at density functional theory

Abedini, Nastaran; Kassaee, M.Z.

doi:10.1007/s00894-022-05202-y

Cited by 2 publications

(2 citation statements)

References 44 publications

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“…[ 29 ] The singlet‐triplet energy gaps (ΔE s‐t = E t − E s ) and band gap (ΔΕ HOMO–LUMO = E LUMO − E HOMO ) are obtained, at 298.15 K and 1.0 atm. [ 30–35 ] The nucleophilicity index ( N ) is calculated as N = E HOMO (Nu) − E HOMO (TCNE) , where tetracyanoethylene (TCNE) is chosen as the reference [ 36,37 ] because it presents the lowest highest occupied molecular orbital (HOMO) energy in a large series of molecules already considered. [ 38 ] The global electrophilicity ( ω ) is computed as

ω = ((), μ^{2} / 2 η),

[ 38 ] where μ is the chemical potential (

μ \approx ((), E_{HOMO} + E_{LUMO}) / 2 true)

and η is the chemical hardness (

η = E_{LUMO} - E_{HOMO} true) .

[ 39–42 ]…”

Section: Methodsmentioning

confidence: 99%

“…[29] The singlet-triplet energy gaps (ΔE s-t = E t À E s ) and band gap (ΔΕ HOMO-LUMO = E LUMO À E HOMO ) are obtained, at 298.15 K and 1.0 atm. [30][31][32][33][34][35] The nucleophilicity index (N) is calculated as N = E HOMO (Nu) À E HOMO (TCNE) , where tetracyanoethylene (TCNE) is chosen as the reference [36,37] because it presents the lowest highest occupied molecular orbital (HOMO) energy in a large series of molecules…”

Section: Introductionmentioning

confidence: 99%

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Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Abedini

Amouzgar

Kassaee

et al. 2023

J of Physical Organic Chem

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The effects of substituting silicon atoms on the stability, geometrical parameters, and electronic properties of cyclo [18]carbon (C 18 ), C 17 Si, and nine isomers of C 16 Si 2 (C 16 Si 2 (0) to C 16 Si 2 (8)) are compared and contrasted at CAM-B3LYP/6-311G* level of theory. Among C 16 Si 2 isomers, the trend of stability (based on total and binding energy*, B3LYP/6-311++G**, WB97XD/6-311G*, and CAM-B3LYP/6-311G* level of theories. Respectively, the highest and lowest band gaps belong to C 18 and C 17 Si, which also have the smallest and largest conductivities. According to the heat of atomization per carbon (ΔH at /C) and heat of formation (ΔH f ), the least thermodynamic stable species, C 16 Si 2 (0), suffers from the highest inter-atomic interaction of neighboring silicon atoms (Si-Si repulsion) and the most thermodynamic stable species, C 16 Si 2 (8), that has the furthest silicon atoms from each other. Theoretical analysis indicates that the most chemically reactive isomers are C 16 Si 2 (1), (3), and (5), which have high nucleophilicity (N = 2.752, 2.665, and 2.573 eV, respectively) and electrophilicity (ω = 0.126, 0.128, and 0.128 eV, respectively). The Si substitution increases the polarizability and activity of rings to interact with their surrounding polar species.

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ω = ((), μ^{2} / 2 η),

[ 38 ] where μ is the chemical potential (

μ \approx ((), E_{HOMO} + E_{LUMO}) / 2 true)

and η is the chemical hardness (

η = E_{LUMO} - E_{HOMO} true) .

[ 39–42 ]…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Abedini

Amouzgar

Kassaee

et al. 2023

J of Physical Organic Chem

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Capture of CO₂by O, S, and Se substituted tripletN‐heterocyclic vinylidenes: a theoretical comparison

Soroudi

Kassaee

2023

J of Physical Organic Chem

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Carbenes are anticipated to capture greenhouse gases. We have compared and contrasted trapping of CO 2 by O, S, and Se substituted singlet (s) and triplet (t) N-heterocyclic vinylidene minima (1 s -3 s and 1 t -3 t , respectively), at M06-2X/6-311++G** level of theory. Unlike many carbenes, our triplet minima (1 t -3 t ) appeared as ground states. Hence, we compared their ability to capture CO 2 . The ease of CO 2 trapping by the scrutinized triplet vinylidenes is:The NBO and AIM results appear consistent with the above trend and our proposed mechanism.

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Estimating structure, stability, and electronic properties on halogenated derivatives of 2-germabicyclo[1.1.1.]pentane-2-ylidenes at density functional theory

Cited by 2 publications

References 44 publications

Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Capture of CO₂by O, S, and Se substituted tripletN‐heterocyclic vinylidenes: a theoretical comparison

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Estimating structure, stability, and electronic properties on halogenated derivatives of 2-germabicyclo[1.1.1.]pentane-2-ylidenes at density functional theory

Cited by 2 publications

References 44 publications

Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Theoretical descriptions of novel silicon analogs of cyclo[18]carbon

Capture of CO2by O, S, and Se substituted tripletN‐heterocyclic vinylidenes: a theoretical comparison

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Capture of CO₂by O, S, and Se substituted tripletN‐heterocyclic vinylidenes: a theoretical comparison