Theoretical evaluation of diffusion coefficients of (Al2O3)n clusters in different bath gases

Sharipov, Alexander S.; Loukhovitski, Boris I.; Tsai, Chuen‐Jinn; Starik, A. M.

doi:10.1140/epjd/e2014-40831-2

Cited by 31 publications

(45 citation statements)

References 48 publications

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“…First, thermodynamics of full electron transfer (ET) from 5 d onto 5 a were analyzed and DFT calculations found them to be very endothermic with Δ G 0 =152.3 kJ mol −1 . The energy of Coulomb interactions in the ion pair was estimated by using their collision diameters calculated as suggested previously (for details, see Section 3 in the Supporting Information) . The rate constant ( k ET ) and activation energy ( E ET ) of the ET were estimated in the framework of the classical Marcus approach by using Equation , in which k B is the Boltzmann constant, Δ G 0 is the free energy of the ET reaction, and λ is the reorganization energy.

true k_{ET} = A \times prefixexp ([], \frac{- {(Δ G^{0} + λ)}^{2}}{4 λ k_{normalB} T}) = A \times prefixexp (- E_{ET} / k_{normalB} T)

…”

Section: Resultsmentioning

confidence: 99%

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

Chulanova

Pritchina

Malaspina

et al. 2016

Chemistry A European J

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The design and synthesis of novel charge-transfer (CT) complexes are of interest for fundamental chemistry and applications to materials science. In addition to the recently described first CT complex with both electron acceptor (A) and donor (D) groups belonging to the 1,2,5-thiadiazole series (1; A: 4-nitro-2,1,3-benzothiadiazole; D: 4-amino-2,1,3-benzothiadiazole), herein novel CT complexes 2 and 3 with 1,2,5-thiadiazoles as both A (4,6-dinitro-2,1,3-benzothiadiazole and [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole) and D (4-amino-2,1,3-benzothiadiazole) were synthesized. The series is completed by complex 4 with [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole as A and phenoxatellurine as D. Structures of complexes 2-4 were characterized by single-crystal X-ray diffraction (XRD), as well as solution and solid-state UV/Vis spectroscopy. Thermodynamics of their formation were obtained by density functional theory (DFT) calculations, their bonding situations were analyzed by quantum theory of atoms in molecules (QTAIM) calculations and dimer model energies of interactions quantified in the framework of the Hirshfeld surface (HS) analysis. With DFT calculations, the largest value of CT between D and A was found for complex 2, with 0.027 e in the XRD structure and 0.150 e in the optimized structure in MeCN. In the UV/Vis spectra, the λ of the CT bands of 2-4 varied in the range λ=517-705 nm. Model energy calculations for 1-4 revealed the importance of both dispersion interactions and hydrogen bonding between D and A as contributors to CT in the crystalline state. In an attempt to enlarge the CT value with bis[1,2,5-thiadiazolo][3,4-b;3',4'-e]pyrazine as A and 4-amino-2,1,3-benzoselenadiazole as D, an unprecedented 1:1 addition reaction was observed upon formation of a C-N bond between atom C7 of D and pyrazine atom N4 of A, accompanied by hydrogen atom transfer from C7 to another pyrazine atom N8 (compound 5). According to DFT calculations, the reaction is a multistep process featuring diradical intermediates and hydrogen atom intramolecular migration over four positions. Molecular and crystal structures of 5 (solvate with toluene) were elucidated by XRD and the crystal structure revealed a rather unusual porous framework.

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true k_{ET} = A \times prefixexp ([], \frac{- {(Δ G^{0} + λ)}^{2}}{4 λ k_{normalB} T}) = A \times prefixexp (- E_{ET} / k_{normalB} T)

…”

Section: Resultsmentioning

confidence: 99%

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

Chulanova

Pritchina

Malaspina

et al. 2016

Chemistry A European J

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“…In general, D 3 Py m -fc resemble three-bladed propellers, while D 4 Py m -fc resemble tetrahedrons. Their collision diameters are 29 Å ( D 3 Py 1 -fc ), 39 Å ( D 3 Py 2 -fc ), 55 Å ( D 3 Py 3 -fc ), 34 Å ( D 4 Py 1 -fc ), 44 Å ( D 4 Py 2 -fc ), and 59 Å ( D 4 Py 3 -fc ). Notably, the ferrocenyl termini form several clusters in which the redox-active sites are located close to each other.…”

Section: Resultsmentioning

confidence: 99%

“Click” Synthesis and Electrochemical Behavior of Ferrocenyl-Terminated Pyridylphenylene Dendrimers

et al. 2020

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The synthetic approach toward ferrocenyl-terminated pyridylphenylene dendrimers based on tri- and tetrafunctional cores via the copper-catalyzed azide-alkyne cycloaddition is presented. Six dendrimers of three generations were synthesized and characterized using NMR spectroscopy, gel permeation chromatography (GPC), and elemental analysis. Cyclic voltammetry (CV) of the dendrimers shows a single quasi-reversible wave. The strong adsorption occurs onto Pt electrodes during CV studies in CH2Cl2, which is reflected by the high i pc/i pa ratio. The modified electrodes coated with a ferrocenyl-terminated dendrimer of the second and third generations are stable toward CH2Cl2 washing and multiple CV scanning and proved to be able to sense Cu+ ions.

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“…The collisional diameter σ and the well depth of the Lennard–Jones potential ε for CF 3 I and C 3 F 7 I species required for RRKM/ME analysis were estimated using the methodology on the basis of computed spatial structures and electric properties (dipole moment and polarizability). The same quantities for Ar were adopted from the work of Cambi et al .…”

Section: Resultsmentioning

confidence: 99%

Direct measurements of C₃F₇I dissociation rate constants using a shock tube ARAS technique

Bystrov

Emelianov

Еремин

et al. 2018

Int J of Chemical Kinetics

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This work presents the first direct experimental study on the thermal unimolecular decomposition of n-C 3 F 7 I. Experiments were performed behind incident and reflected shock waves using the atomic resonance absorption spectroscopy (ARAS) technique on a resonant line of atomic iodine at 183.04 nm. The reaction C 3 F 7 I + Ar → C 3 F 7 + I + Ar (1) was studied at specific temperature (800-1200 K) and pressure (0.6-8.3 bar) ranges. Under experimental conditions, the obtained values of the rate constant at temperatures below 950 K are close to the high-pressure limit; however, considering theoretical calculations, the influence of pressure on the rate constant at elevated temperatures remains noticeable. The resulting value of the experimental rate constant of reaction 1 is presented in the following Arrhenius form: 1st (±30%) = 1.05 × 10 14 exp(−200.4 kJ ⋅ mol −1 ∕ ) (s −1 ) Experimental data were found to correlate with the results of the Rice-Ramsperger-Kassel-Marcus -master equation analysis based on quantum-chemical calculations.The following low-and high-pressure limiting rate coefficients were obtained over the temperature range T = 300-3000 K: 0 ( −C 3 F 7 I + Ar ) = 8.849 × 10 19 −1.444 exp (−11, 454.4∕ ) (cm 3 mol −1 s −1 ) and ∞ ( −C 3 F 7 I ) = 9.676 × 10 16 −0.378 exp (−26, 956.8∕ ) (s −1 )with the center broadening factor F c = 0.119. K E Y W O R D Satomic resonance absorption spectroscopy, chemical kinetics, density functional theory, dissociation rate constant, perfluoropropyl iodide, Rice-Ramsperger-Kassel-Marcus/master equation, shock tube 206

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Theoretical evaluation of diffusion coefficients of (Al2O3)n clusters in different bath gases

Cited by 31 publications

References 48 publications

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

“Click” Synthesis and Electrochemical Behavior of Ferrocenyl-Terminated Pyridylphenylene Dendrimers

Direct measurements of C₃F₇I dissociation rate constants using a shock tube ARAS technique

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Theoretical evaluation of diffusion coefficients of (Al2O3)n clusters in different bath gases

Cited by 31 publications

References 48 publications

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction

“Click” Synthesis and Electrochemical Behavior of Ferrocenyl-Terminated Pyridylphenylene Dendrimers

Direct measurements of C3F7I dissociation rate constants using a shock tube ARAS technique

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Direct measurements of C₃F₇I dissociation rate constants using a shock tube ARAS technique