Functionalized nona-silicide [Si<sub>9</sub>R<sub>3</sub>] Zintl clusters: a new class of superhalogens

Sinha, Swapan; Jena, P.; Giri, Santanab

doi:10.1039/d2cp02619h

Cited by 7 publications

(10 citation statements)

References 58 publications

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“…The VDE is determined by taking the difference between the energies of the anion and the corresponding neutral species possessing the anion geometry, as shown in equation 1. [4,57,60]…”

Section: Dft Calculationsmentioning

confidence: 99%

“…The electron-withdrawing groups pull the electron density of the clusters toward themselves, and hence, the propensity of clusters to accept electrons increases, which amplifies the VDE values. [60] In contrast, the electron-donating group (À CH 3 ) decreases the VDE values slightly. For most anions, it can be noted that À NCS and À CF 3 increase the VDE values to the maximum extent, indicating greater stability of the clusters with these substituents.…”

Section: Vertical Detachment Energy (Vde)mentioning

confidence: 99%

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Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Sharma

Thomas

Gupta

2023

Batteries & Supercaps

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Calcium‐ion batteries (CIBs) are promising energy storage systems, but the unavailability of adept electrolytes has hindered their development. In this work, a range of silaborane clusters ( normalSnormalinormalBn-1Hn- ${{{\rm S}{\rm i}{\rm B}}_{n-1}{{\rm H}}_{n}^{-}}$ ; n=5–15) were investigated using density functional theory (DFT) at ωB97XD3/6‐311+G(d,p) level of theory. The vertical detachment energy (VDE), electrochemical stability window (ESW) and binding energy (BE) of the silaboranes were computed at the same level of DFT. A methodology based on molecular electrostatic potential surface analysis was designed to locate the most suitable binding site for calcium ions on the clusters. DFT results show that the SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ cluster turns out to be superior to other candidates. Effect of substitution on silaboranes ( normalSnormalinormalBn-1Hn-1 ${{{\rm S}{\rm i}{\rm B}}_{n-1}{{\rm H}}_{n-1}}$ R− R=−CH3, −NCS, −CF3, −F and −Cl) was computed. −NCS and −CF3 substituted SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ ions were found to be the best from DFT. Ab initio molecular dynamics (AIMD) studies were performed to explore the interactions between silaborane‐based electrolytes and the Ca anode. AIMD results highlight the decomposition of −NCS and −CF3 substituted SiB11 normalH12- ${{{\rm H}}_{12}^{-}}$ on Ca anode. DFT and AIMD studies reveal that −CH3 substituted silaborane‐based Ca‐salt (Ca(SiB11H11CH3)2) is the promising electrolyte for CIBs.

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“…The VDE is determined by taking the difference between the energies of the anion and the corresponding neutral species possessing the anion geometry, as shown in equation 1. [4,57,60]…”

Section: Dft Calculationsmentioning

confidence: 99%

Section: Vertical Detachment Energy (Vde)mentioning

confidence: 99%

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Sharma

Thomas

Gupta

2023

Batteries & Supercaps

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“…cluster can be explained using the Wade-Mingos and Jellium electronic shell closure rules, respectively. [26,64] It possesses a Nido structure (follow 4n + 4 rule, where n is the number of vertices in the cluster, here n = 9 and valence electrons of Si = 4) and contains a stable 40 (9x4 + 4) magic number of electrons. The electronic configuration of Si 9…”

Section: àmentioning

confidence: 99%

“…[23][24][25] Zintl cluster is polyatomic versatile multianion species belong to a main group compound that exhibits unique reactivity and can participate in diverse chemical transformations. [26][27][28][29][30][31][32] Recently, various studies shown that the nonagermanium based Zintl cluster (Ge 9 ) can be act as a nucleophile due to its presence of external lone pairs. [25,[32][33][34][35] Therefore, one promising avenue is using Zintl clusters as potential cleaving agent for disulfide bonds.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Zintl Cluster Mediated Disulfide Bond Separation: A DFT Study

Sinha,

Giri

2023

ChemistrySelect

Self Cite

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Disulfide bond cleavage plays a crucial role in various chemical and biological processes. In recent years, developing novel and efficient catalysts for disulfide bond cleavage has garnered significant attention. This manuscript presents a comprehensive density functional theory (DFT) study on the separation of a disulfide bond by a well‐known Nona‐silicide Zintl cluster, Si94−. It is a single‐step exothermic reaction process that proceeds via the SN2 mechanism. This study also investigates the electronic activity, electron transfer process, and other electronic properties associated with the disulfide bond dissociation by the Si9‐Zintl cluster using the M06‐2X computational method.

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“…They can be utilized to create uncommon CT salts whose counterparts have a low electron affinity (EA). In silico design and characterization of superalkalis based on Zintl ions and the superatom compounds with an NLO response have been reported by some research groups along with Zintl clusters as a new class of superhalogens which can be seen in the literature ( Reddy et al, 2018b , Reddy et al, 2018a ; Sun et al, 2018 ; Sinha et al, 2022 ).…”

Section: Introductionmentioning

confidence: 99%

Recent advances in in silico design and characterization of superalkali-based materials and their potential applications: A review

et al. 2022

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In the advancement of novel materials, chemistry plays a vital role in developing the realm where we survive. Superalkalis are a group of clusters/molecules having lower ionization potentials (IPs) than that of the cesium atom (3.89 eV) and thus, show excellent reducing properties. However, the chemical industry and material science both heavily rely on such reducing substances; an in silico approach-based design and characterization of superalkalis have been the focus of ongoing studies in this area along with their potential applications. However, although superalkalis have been substantially sophisticated materials over the past couple of decades, there is still room for enumeration of the recent progress going on in various interesting species using computational experiments. In this review, the recent developments in designing/modeling and characterization (theoretically) of a variety of superalkali-based materials have been summarized along with their potential applications. Theoretically acquired properties of some novel superalkali cations (Li3+) and C6Li6 species, etc. for capturing and storing CO2/N2 molecules have been unveiled in this report. Additionally, this report unravels the first-order polarizability-based nonlinear optical (NLO) response features of numerous computationally designed novel superalkali-based materials, for instance, fullerene-like mixed-superalkali-doped B12N12 and B12P12 nanoclusters with good UV transparency and mixed-valent superalkali-based CaN3Ca (a high-sensitivity alkali-earth-based aromatic multi-state NLO molecular switch, and lead-founded halide perovskites designed by incorporating superalkalis, supersalts, and so on) which can indeed be used as a new kind of electronic nanodevice used in designing hi-tech NLO materials. Understanding the mere interactions of alkalides in the gas and liquid phases and the potential to influence how such systems can be extended and applied in the future are also highlighted in this survey. In addition to offering an overview of this research area, it is expected that this review will also provide new insights into the possibility of expanding both the experimental synthesis and the practical use of superalkalis and their related species. Superalkalis present the intriguing possibility of acting as cutting-edge construction blocks of nanomaterials with highly modifiable features that may be utilized for a wide-ranging prospective application.

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Functionalized nona-silicide [Si₉R₃] Zintl clusters: a new class of superhalogens

Abstract: Superatoms, due to their various applications in redox and materials chemistry, have been a major topic of study in cluster science. Superhalogens constitute a special class of superatoms that mimic...

Cited by 7 publications

References 58 publications

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Insights into the Zintl Cluster Mediated Disulfide Bond Separation: A DFT Study

Recent advances in in silico design and characterization of superalkali-based materials and their potential applications: A review

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Functionalized nona-silicide [Si9R3] Zintl clusters: a new class of superhalogens

Abstract: Superatoms, due to their various applications in redox and materials chemistry, have been a major topic of study in cluster science. Superhalogens constitute a special class of superatoms that mimic...

Cited by 7 publications

References 58 publications

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB11H11CH3)2 as the Promising Electrolyte for Calcium‐Ion Batteries

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB11H11CH3)2 as the Promising Electrolyte for Calcium‐Ion Batteries

Insights into the Zintl Cluster Mediated Disulfide Bond Separation: A DFT Study

Recent advances in in silico design and characterization of superalkali-based materials and their potential applications: A review

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Product

Resources

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Functionalized nona-silicide [Si₉R₃] Zintl clusters: a new class of superhalogens

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries

Two Layers of Computational Screening on Silaborane‐based Clusters Filter Ca(SiB₁₁H₁₁CH₃)₂ as the Promising Electrolyte for Calcium‐Ion Batteries