Electronic structure and physical properties of MiXi clusters (M = B, Al; X = N, P; i = 1, 2, 3): Ab initio study

Ončák, Milan; Srnec, Martin

doi:10.1002/jcc.20781

Cited by 15 publications

(2 citation statements)

References 57 publications

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“…The potential energy surface (PES) of NB 6 – suggested that the planar hexacoordinate nitrogen species NB 6 – is not stable . The structure and property of (BN) n ( n = 2−11) have been investigated theoretically,[] among which researchers found the stability of cyclic B 3 N 3 isomer with D 3h symmetry is ascribed mainly to its aromaticity . The structure and stability of (BN) n ( n = 2–4) were investigated by ab initio calculations.…”

Section: Introductionmentioning

confidence: 99%

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers

Cui

Wang

Shao

et al. 2013

Int. J. Quantum Chem.

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We perform a systematic study on the geometry, stability, nature of bonding, and potential energy surface of low-lying isomers of planar and cyclic B n N 2 (n ¼ 1À6) at the CCSD(T)/ 6-311þG(d)//B3LYP/6-311þG(d) level. B n N 2 (n ¼ 2À4) clusters are structurally similar to pure boron clusters. The evolution of the binding energy per atom, incremental binding energy, and second-order difference of total energy with the size of B n N 2 reveals that the lowest energy isomer of B 3 N 2 has high stability. B 5 N 2 and B 6 N 2 possess p-aromaticity according to Hü ckel (4n þ 2) rule. The aromaticity of some isomers of B 4 N 2 and B 6 N 2 is examined based on their valence molecular orbitals. At the CCSD(T)/6-311þG(d)//B3LYP/6-311þG(d) level, several B 2 N 2 , B 3 N 2 , B 4 N 2 , and B 5 N 2 isomers are predicted to be stable both thermodynamically and kinetically, and detectable in future experiments.

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Section: Introductionmentioning

confidence: 99%

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers

Cui

Wang

Shao

et al. 2013

Int. J. Quantum Chem.

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“…Then, the TSR mechanism can provide a pathway with low activation energy or alter the product composition and yield ratio. Oncák et al [12] studied the hydroxylation of alkanes by reagents HOF and HOCl in the gas phase upon acid catalysis but only singlet pathways were investigated (without considering TSR).…”

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confidence: 99%

DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system

Litvinenko

Rudakov

2012

Theor Exp Chem

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The DFT method was used to study gas-phase chlorination reactions CH 4 + HOCl (1) and CH 4 + HOCl + H 2 O (2). These reactions entail singlet-triplet (s®t) preactivation of HOCl and terminate in a reverse t®s transition. At 298 K, the barrier DG t ¹ for reaction (2) is higher than for reaction (1) by 1.5 kcal/mol, while the singlet transition state TS s -2 lies higher than TS t -2 by DG ¹ = 21.4 kcal/mol. The reactions of alkanes (RH) with chlorine in the gas phase and in acid media such as Cl 2 -CH 3 CO 2 H-H 2 SO 4 have a radical chain mechanism initiated by light or thermally [1]. In superacids, electrophilic chlorination of RH by Cl + ions takes place [2]. In previous work [3, 4], we were the first to study the chlorination of alkanes by hypochlorous acid in water: (1) RH + HOCl ® RCl + H 2 O. The kinetic equation -(d[RH]/dt) = k[RH][HOCl] holds in three chlorinating systems, namely, Cl 2 /H 2 O, Cl 2 + Hg 2+ /H 2 O, and HOCl/H 2 O. The values of k are equal for equal [HOCl] and identical for reactions in the light and dark. The primary and tertiary C-H bonds in isobutane (CH 3 ) 3 CH are chlorinated in parallel to give (CH 3 ) 2 CHCH 2 Cl and (CH 3 ) 3 CCl. (CH 3 ) 2 CHCH 2 Cl is further chlorinated, while (CH 3 ) 3 CCl is rapidly hydrolyzed to give (CH 3 ) 3 COH. A similarity was found in the substrate selectivity and kinetic isotope effect (KIE) (c-C 6 H 12 /c-C 6 D 12 ) for reaction (1) and the reaction RH + OH • ® R • + H 2 O in the gas phase. Thus, the ratio of the rate constants ethane : propane : isobutane is 0.14 : 1 : 3.6, while the KIE = 2.9 ± 0.2 for HOCl in water at 70°C and 0.24 : 1 : 2.1 and KIE = 2.6 ± 0.2 for OH • in the gas phase at 25°C. We note that the reaction of RH + OH • in water is complicated by a cage effect [4,5] and is not suitable for comparison with reaction (1).These findings permit us to exclude species Cl • , Cl 2 , Cl + , Cl -¼Hg 2+ , and Cl + ¼OH 2 as possible reagents and conclude that reaction (1) proceeds as a molecular chlorination by HOCl and begins with reagent preactivation entailing the conversion of singlet HOCl into triplet HO • Cl • , while the C-H bond is broken by the action of the OH • group of the HO • Cl • diradical [4].In the present work, for a comparison with the kinetic data for reaction (1) in water and to check the hypothesis of a singlet-triplet preactivation of the reagent, we studied the mechanism of the chlorination of methane by HOCl molecules in the gas phase by the density functional (DFT) method for variants with a bimolecular (reaction (1)) and trimolecular reaction (with the participation of a water molecule)(2) RH + HOCl + H 2 O ® RCl + 2H 2 O.

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Evaluating Electronic Properties of Self‐Assembled Indium Phosphide Nanomaterials as High‐Efficient Solar Cell

Zhao,

Jin,

Lin

et al. 2024

Int J of Quantum Chemistry

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Geometries and electronic properties associated with relative stabilities and energy gaps of porous (InP)12n (n = 1–12) nanoclusters (NCs) (nanowires and nanosheets) are systemically studied by density functional method. The relative stabilities of (InP)12n NCs through the calculated fragmentation energies and cluster‐binding energies are determined and discussed. Interestingly, the calculated energy gaps of (InP)12n nanowires and nanosheets are localized at regions of visible light energy ranges. (InP)12n are relatively wide‐band semiconductor solar energy nanomaterial. The calculated density of states reveals large‐sized porous (InP)12n nanosheets and nanowires with narrow pore size distribution and slight thickness and a large surface area manifest ultrahigh specific capacitance of trapping solar light energies and high light‐to‐electricity conversion efficiencies in solar energy absorption or conversion or photovoltaicsm. Particularly, (InP)12n NCs maintain their elemental properties of individual (InP)12 clusters in the energy gaps of (InP)12n (n > 4). NCs are almost independent of variable sizes. Specifically, the size‐dependent charge transfers of In atoms in (InP)12n NCs exhibit that ionic and covalent bonding exist in (InP)12n NCs and can stabilize (InP)12n NCs. Comparison with experiment results available is made.

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Electronic structure and physical properties of M_iX_i clusters (M = B, Al; X = N, P; i = 1, 2, 3): Ab initio study

Cited by 15 publications

References 57 publications

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers

DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system

Evaluating Electronic Properties of Self‐Assembled Indium Phosphide Nanomaterials as High‐Efficient Solar Cell

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Electronic structure and physical properties of MiXi clusters (M = B, Al; X = N, P; i = 1, 2, 3): Ab initio study

Cited by 15 publications

References 57 publications

Geometry, stability, and isomerization of B n N2 (n = 1−6) isomers

Geometry, stability, and isomerization of B n N2 (n = 1−6) isomers

DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system

Evaluating Electronic Properties of Self‐Assembled Indium Phosphide Nanomaterials as High‐Efficient Solar Cell

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Product

Resources

About

Electronic structure and physical properties of M_iX_i clusters (M = B, Al; X = N, P; i = 1, 2, 3): Ab initio study

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers

Geometry, stability, and isomerization of B _n N₂ (n = 1−6) isomers