Structure and Bonding in CE<sub>5</sub><sup>−</sup> (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

Ravell, Estefanía; Jalife, Said; Barroso, Jorge; Orozco‐Ic, Mesías; Hernández-Juárez, Gerardo; Ortíz‐Chi, Filiberto; Pan, Sudip; Cabellos, José Luis; Merino, Gabriel

doi:10.1002/asia.201800261

Cited by 37 publications

(23 citation statements)

References 63 publications

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“…Several algorithms to explore the potential/free energy surface coupled to an any electronic structure package have been successfully employed so far, such as AIRSS approach, [ 98 ] simulated annealing, [ 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 104 ], kick methodology [ 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 , 113 , 114 , 115 , 116 ], and genetic algorithms [ 9 , 21 , 33 , 112 , 116 , 117 , 118 , 119 ], among others.…”

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

et al. 2021

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Lowest-energy structures, the distribution of isomers, and their molecular properties depend significantly on geometry and temperature. Total energy computations using DFT methodology are typically carried out at a temperature of zero K; thereby, entropic contributions to the total energy are neglected, even though functional materials work at finite temperatures. In the present study, the probability of the occurrence of one particular Be4B8 isomer at temperature T is estimated by employing Gibbs free energy computed within the framework of quantum statistical mechanics and nanothermodynamics. To identify a list of all possible low-energy chiral and achiral structures, an exhaustive and efficient exploration of the potential/free energy surfaces is carried out using a multi-level multistep global genetic algorithm search coupled with DFT. In addition, we discuss the energetic ordering of structures computed at the DFT level against single-point energy calculations at the CCSD(T) level of theory. The total VCD/IR spectra as a function of temperature are computed using each isomer’s probability of occurrence in a Boltzmann-weighted superposition of each isomer’s spectrum. Additionally, we present chemical bonding analysis using the adaptive natural density partitioning method in the chiral putative global minimum. The transition state structures and the enantiomer–enantiomer and enantiomer–achiral activation energies as a function of temperature evidence that a change from an endergonic to an exergonic type of reaction occurs at a temperature of 739 K.

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Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

et al. 2021

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“…Moreover, the calculated total energy of the cluster demands a high level of quantum mechanical methodology to produce reliable energies. Despite that, several algorithms coupled with DFT have been employed to search for the lowest energy structures on the potential energy surface of atomic clusters, such as the kick methodology [ 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 ] and genetic algorithms [ 43 , 78 , 79 , 80 , 81 ]. Our computational procedure to elucidate the lowest energy consisted of a hybrid genetic algorithm called GALGOSON [ 43 , 47 ].…”

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

Effects of Temperature on Enantiomerization Energy and Distribution of Isomers in the Chiral Cu13 Cluster

et al. 2021

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In this study, we report the lowest energy structure of bare Cu13 nanoclusters as a pair of enantiomers at room temperature. Moreover, we compute the enantiomerization energy for the interconversion from minus to plus structures in the chiral putative global minimum for temperatures ranging from 20 to 1300 K. Additionally, employing nanothermodynamics, we compute the probabilities of occurrence for each particular isomer as a function of temperature. To achieve that, we explore the free energy surface of the Cu13 cluster, employing a genetic algorithm coupled with density functional theory. Moreover, we discuss the energetic ordering of isomers computed with various density functionals. Based on the computed thermal population, our results show that the chiral putative global minimum strongly dominates at room temperature.

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“…[18][19][20][21][22] Doped hydrocarbons or carbon clusters with lithium, 23 beryllium/boron, 24,25 boron, [26][27][28][29][30] nitrogen, 31 silicon, 32 phosphorus, 33,34 and late transition metals 35 with a ptC, ptB, ptN, ptSi, or ptP atom are also reported. It is worth to note here that planar penta, [36][37][38][39][40][41][42][43] hexa, [44][45][46][47][48] and hepta 49,50 coordinated carbon compounds are also actively pursued due to the potential implications of these molecules in making new materials. 51 In this work, we explored the dissociation pathways of three different isomers of C 7 H 2 , which contain a ptC atom.…”

Section: Introductionmentioning

confidence: 99%

From High-Energy C₇H₂ Isomers with A Planar Tetracoordinate Carbon Atom to An Experimentally Known Carbene

2018

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In this work, we use high-level ab initio procedures to show that the high-energy isomers of C 7 H 2 with a planar tetracoordinate carbon (ptC) atom serve as reactive intermediate leading to the formation of an experimentally known ring-chain carbene, 1-(buta-1,3-diynyl)cyclopropenylidene (2). Among the experimentally known isomers of C 7 H 2 , the latter is the only low-lying ring-chain carbene identified by Fourier-transform microwave spectroscopy. Here we investigate the ring opening pathways of C-C single bonds connected to the ptC atom in three different C 7 H 2 isomers using coupled-cluster and density functional theory methods. These three isomers [ptC1 (C 2v ; X 1 A 1 ), ptC2 (C s ; X 1 A ), and ptC3 (C s ; X 1 A )] are found to be local minima on the C 7 H 2 potential-energy surface at both CCSD(T)/cc-pVTZ and B3LYP/6-311+G(d,p) levels of theory. The transition states and minimum-energy pathways connecting the reactants (ptC isomers) and the products have been found via intrinsic reaction coordinate calculations at the B3LYP/6-311+G(d,p) level of theory. The high-energy ptC isomers (ptC2 and ptC3) lead to the formation of 2, whilst the low-energy ptC isomer, ptC1, rearranges to a bicyclic carbene, bicyclo[4.1.0]hepta-4,6-diene-2-yne-7-ylidene (6). In the latter, we note that both the reactant and the product are yet to be identified in the laboratory. Relative energies, activation energies, reaction energies, and nucleus independent chemical shift values have been calculated to access the thermodynamic and kinetic stabilities and the aromatic nature of these peculiar molecules. Rotational and centrifugal distortion constants have also been estimated for all ptC isomers, which may assist the efforts of microwave spectroscopists.

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Structure and Bonding in CE₅⁻ (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

Cited by 37 publications

References 63 publications

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Effects of Temperature on Enantiomerization Energy and Distribution of Isomers in the Chiral Cu13 Cluster

From High-Energy C₇H₂ Isomers with A Planar Tetracoordinate Carbon Atom to An Experimentally Known Carbene

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Structure and Bonding in CE5− (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

Cited by 37 publications

References 63 publications

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures

Effects of Temperature on Enantiomerization Energy and Distribution of Isomers in the Chiral Cu13 Cluster

From High-Energy C7H2 Isomers with A Planar Tetracoordinate Carbon Atom to An Experimentally Known Carbene

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Product

Resources

About

Structure and Bonding in CE₅⁻ (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

From High-Energy C₇H₂ Isomers with A Planar Tetracoordinate Carbon Atom to An Experimentally Known Carbene