Radiation-induced transformations of difluoromethane in noble gas matrices

Sosulin, Ilya S.; Feldman, Vladimir I.

doi:10.1016/j.radphyschem.2021.109672

Cited by 5 publications

(3 citation statements)

References 41 publications

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“…Recently we applied the matrix isolation technique for systematic investigations of mechanisms of radiation-induced transformations of fluoroform, difluoromethane and their complexes with atmospherically relevant species at the molecular level. 27–29 As demonstrated previously, 30 this approach may be generally useful for modeling basic features of the transformations of various molecules relevant to atmospheric chemistry and astrochemistry. Its extension may be also useful for the studies of the reactions between photolysis or radiolysis products (radicals, carbenes) and atomic oxygen.…”

Section: Introductionmentioning

confidence: 83%

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Sosulin

Shiryaeva

Tyurin

et al. 2023

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 83%

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Sosulin

Shiryaeva

Tyurin

et al. 2023

Phys. Chem. Chem. Phys.

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“…After the discovery of the first noble gas compound, several other compounds with heavier noble gases have been reported in the literature; however, the first chemically bonded argon compound, viz., HArF, is reported only in the year 2000. These pioneering works in this field motivated both experimentalists and theoreticians in exploring the possibility of the existence of novel compounds involving chemically bonded Ng atoms. − …”

Section: Introductionmentioning

confidence: 99%

Superstrong Chemical Bonding of Noble Gases with Oxidoboron (BO⁺) and Sulfidoboron (BS⁺)

2022

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Inspired by the overwhelming exploration of noble gas–boron (Ng–B) bond containing chemical compounds, the stability of the Ng bound BY+ and AlY+ (Y = O and S) has been investigated by using various ab initio based quantum chemical methods. Ng atoms are found to form exceptionally strong bonds with BO+ species in the predicted NgBO+ (Ng = He–Rn) complexes with remarkably high Ng–B dissociation energies ranging from 138.0 to 462.2 kJ mol–1 for the He–Rn series. It is the highest ever Ng–B binding energy in conjunction with the smallest Ng–B bond length for any of the cationic species involving a Ng–B bond as reported until today. More importantly, the calculated Ng–B bond lengths have been found to be much lower than the respective covalent limits in both NgBO+ and NgBS+ ions. The electronegativity difference between O and S atoms has been reflected nicely in the Ng–B and Ng–Al binding energies, which are found to be 91.9–346.5, 9.6–169.2, and 6.8–142.1 kJ mol–1 in NgBS+, NgAlO+, and NgAlS+, respectively. The strong covalent bonding between Ng and B/Al atoms in the predicted chemical systems has also been supported by the natural bonding orbital (NBO) and electron density based atoms-in-molecule (AIM) analysis. In addition, the energy decomposition analysis (EDA) in combination with the natural bond orbital for chemical valence (NOCV) indicates that the orbital interaction term is the prime contributor to the total attraction energy in the Ng–B and Ng–Al bonds. Furthermore, Ng–B and Ng–Al bonding can be assessed using the donor–acceptor model where the σ-electron donation that takes place from Ng (HOMO) → XY+ (LUMO) (X = B and Al; Y = O and S) is the major contributor to the orbital interaction energy. All the computational results along with the very recent experimental observation of ArOH+ and NgMX (Ng = Ar–Xe; M = Cu, Ag, Au; X = F, Cl) clearly indicate that it might be possible to synthesize and characterize these superstrong complexes, NgXY+ (Ng = He–Rn; X = B and Al; Y = O and S), under suitable experimental technique(s).

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“…The domain of the noble gas chemistry has expanded after the discovery of the first stable molecule of argon (HArF) characterized using the infrared absorption spectroscopic technique supported by ab initio quantum chemical calculations by Räsänen and co-workers in 2000. , Following this revolutionized work, various noble gas-containing neutral and charged chemical compounds − ,− have been predicted theoretically and prepared via suitable experimental techniques. In general, these metastable compounds are obtained by inserting a noble gas atom into a stable molecule having either astronomical significance such as HCO + , HCS + , and HN 2 + or environmental importance such as HOX (X = F, Cl, and Br) and H 3 O + .…”

Section: Introductionmentioning

confidence: 99%

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

et al. 2022

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Recent theoretical prediction and experimental identification of fluorinated noble gas cyanides and isocyanides motivate us to explore a unique novel series of neutral noble gasinserted heavier cyanofluoride isomers, FNgYSi and FNgSiY (Ng = Kr, Xe, and Rn; Y = N and P), theoretically using quantum chemical calculations. The concerned minima and saddle point geometries have been optimized using DFT, MP2, and CCSD(T) methods. The precursor molecule FSiY is more stable than its isomer FYSi, and the stability order is found to be reversed after the insertion of a noble gas (Ng) atom into them which is in contrast to the previously reported FCN/FNC systems where the stability order in the precursors remains intact after the insertion of a Ng atom into them. The predicted FNgYSi molecules are metastable in nature as they are kinetically stable but thermodynamically unstable with respect to the global minima products (FYSi and Ng). All the calculations for the corresponding FNgSiY molecules clearly indicate that the less stable FNgSiY behaves similarly to the FNgYSi in all respects. The energetics, force constant, and spectroscopic data strongly reinforce the possibility of occurrence of these predicted FNgYSi and FNgSiY molecules which might be experimentally realized under suitable cryogenic condition(s).

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Radiation-induced transformations of difluoromethane in noble gas matrices

Cited by 5 publications

References 41 publications

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Superstrong Chemical Bonding of Noble Gases with Oxidoboron (BO⁺) and Sulfidoboron (BS⁺)

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

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Radiation-induced transformations of difluoromethane in noble gas matrices

Cited by 5 publications

References 41 publications

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Reactions of oxygen atoms with fluoroform and its radiolysis products: matrix isolation and ab initio study

Superstrong Chemical Bonding of Noble Gases with Oxidoboron (BO+) and Sulfidoboron (BS+)

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

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Superstrong Chemical Bonding of Noble Gases with Oxidoboron (BO⁺) and Sulfidoboron (BS⁺)