Molecular structure, linear and nonlinear optical properties of some cyclic phosphazenes: A theoretical investigation

Hadji, Djebar; Rahmouni, Abdelkader

doi:10.1016/j.molstruc.2015.10.033

Cited by 33 publications

(8 citation statements)

References 61 publications

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“…The performances of traditional and novel long-range corrected exchange-correlation (XC) functionals, B3LYP [10], ωB97X-D [16], CAM-B3LYP [12], LC-BLYP [13], M05-2X [17], and M06-2X [15], were explored. Long-range corrected XC functionals have been shown to be at least as competitive and often more reliable with respect to traditional DFT functionals to calculate linear and nonlinear responses [18][19][20][21][22][23][24][25][26][27][28]. For , we concentrated on its two invariants, the mean polarizability ⟨ ⟩ and the polarizability anisotropy Δ .…”

Section: Methodsmentioning

confidence: 99%

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

Hadji

Champagne

2019

Chemistry Africa

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The electrical properties (dipole moment, polarizability, and first hyperpolarizabilities) of anhydride derivatives are studied using theoretical chemistry methods. Several DFT XC functionals have been used while reliable atomic basis sets have been selected for their evaluations. The variations of (hyper)polarizabilities as a function of the anhydride structure are consistent among the different functionals, which facilitates the deduction of structure-property relationships. It has been observed that (1) The dipole moment of maleic anhydride (2) increases when adding a methyl group (3) and even more when fusing a phenyl ring to get phthalic anhydride (1), in good agreement with experiment. (2) The average polarizability is mostly driven by the molecular size while the polarizability anisotropy presents more subtle variations as a function of the compound. (3) For 1 and 2, the calculated polarizability tensor components are in close agreement with the experimental data. (4) To a good extend, the HRS first hyperpolarizabilities follow the same ordering as the polarizability anisotropy. (5) The EFISHG first hyperpolarizabilities exhibit a completely different ordering while its sign depends on the orientation of the CO double bonds. Finally, since the first hyperpolarizability values of these anhydride derivatives are of moderate amplitude, like those of amino acids, several design strategies have been discussed for achieving their enhancement.

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Section: Methodsmentioning

confidence: 99%

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

Hadji

Champagne

2019

Chemistry Africa

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“…12). From our previous studies [59][60][61],it can be state that the CAM-B3LYP functional has shown to predict reliable hyperpolarizability of different compounds.In case of the presence of the , and using the6-311+G(d) and aug-cc-pVDZbasis sets, the B3LYP functional givesthe lowest values of the mean polarizabilities . On the other hand, the bisImClshows the highest β HRS values (β HRS = 516.6 a.u.)…”

Section: Electrical Propertiesmentioning

confidence: 99%

Synthesis, NMR, Raman, thermal and nonlinear optical properties of dicationic ionic liquids from experimental and theoretical studies

Hadji

Haddad

Brandán

et al. 2020

Journal of Molecular Structure

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HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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“…One method of preparing the parent polymer, [PCl 2 N] n , is through a melt ring-opening polymerization (ROP) of [PCl 2 N] 3 . Subsequently, replacing the chlorine atoms with various (R) substituents, the functionalized derivatives become versatile and find wide applications in diverse fields, including elastomers, fire-resistant materials, optical materials, − protective coatings, conductors, , interpenetrating polymer networks, nanofibers, catalysts, lubricants, and biomedical materials. ,, Researchers have extensively examined this reaction and alternative reactions involving Cl 3 PNSiMe 3 through experimentation in an attempt to comprehend its underlying mechanism. − However, despite their efforts, the intricacies of the chlorophosphazene ROP reaction remain inadequately understood.…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations

Xue,

Salmon,

Ramlo

et al. 2024

Macromolecules

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The most popular method to synthesize polychlorophosphazenes, the parent of a prominent class of inorganic polymers, is the ring-opening polymerization (ROP) of [PCl 2 N] 3 . In contrast to the accepted (S N 1-initiated) ROP mechanism that begins with heterolytic P−Cl bond cleavage in [PCl 2 N] 3 , our quantum mechanical (QM) calculations suggest that the ROP can proceed through a S N 2-like route in which one [PCl 2 N] 3 can be attacked by a neighboring [PCl 2 N] 3 and hence transform through a four-center transition state (4C PNPCl TS), yielding a cyclic chlorophosphazene with a linear tail, termed a "tadpole". Meanwhile, two [PCl 2 N] 3 molecules can morph into [PCl 2 N] 6 (RR expansion) through a different four-center transition state (4C PNPN TS) without the assistance of a bridging chlorine. As the activation energy of these processes follows the trend tadpole backbite < chain branching < ROP initiation ≤ RR initiation = RR expansion < chain propagation (all within 241.2 ± 16 kJ/mol), the ROP and RR mechanisms compete toward product formation. Not only does our pioneering QM calculations unveil the pivotal role of the bridging chlorine in the S N 2 mechanism, it also explains its effect on reactivity of [PCl 2 N] 3 species, underscoring the significance of halogen substituents in modulating polymerization. By comprehensively examining the ROP, RR, linear propagation, and ring closure processes, we attempt to resolve long-standing queries in chlorophosphazene research, elucidating the wide variability in reaction pot products and the necessity of halogen substituents in specific processes. Thus, this work characterizes a variety of four-center transition states for the first time and introduces a novel mechanistic process for polymerization. Finally, our work provides an explanation of the existence of the chlorinated tadpole.

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Molecular structure, linear and nonlinear optical properties of some cyclic phosphazenes: A theoretical investigation

Cited by 33 publications

References 61 publications

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

Synthesis, NMR, Raman, thermal and nonlinear optical properties of dicationic ionic liquids from experimental and theoretical studies

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations

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Molecular structure, linear and nonlinear optical properties of some cyclic phosphazenes: A theoretical investigation

Cited by 33 publications

References 61 publications

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

First Principles Investigation of the Polarizability and First Hyperpolarizability of Anhydride Derivatives

Synthesis, NMR, Raman, thermal and nonlinear optical properties of dicationic ionic liquids from experimental and theoretical studies

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl2N]3 Using Quantum Mechanical Calculations

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Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations