Neutralization of solvated protons and formation of noble-gas hydride molecules: matrix-isolation indications of tunneling mechanisms?
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Citations
Atypical compounds of gases, which have been called ‘noble’
Noble-gas hydrides: new chemistry at low temperatures.
On theoretical predictions of noble-gas hydrides.
Insertion of noble gas atoms into cyanoacetylene: an ab initio and matrix isolation study.
Comparison of Hydrogen and Gold Bonding in [XHX](-) , [XAuX](-) , and Isoelectronic [NgHNg](+) , [NgAuNg](+) (X=Halogen, Ng=Noble Gas).
References
Formation and characterization of neutral krypton and xenon hydrides in low-temperature matrices
Chemical compounds formed from diacetylene and rare-gas atoms: HKrC4H and HXeC4H
Infrared spectroscopic evidence for the stabilization of HArn+ in solid argon at 14 K
On microwave discharge sources of new chemical species for matrix‐isolation spectroscopy and the identification of charged species
Hydrogen Dibromide Radical: Infrared Detection through the Matrix Isolation Technique
Related Papers (5)
Frequently Asked Questions (16)
Q2. How many pulses of HBr were used to photolyze?
The 193-nm radiation of an excimer laser MSX-250, MPB, pulse energy density 10 mJ cm−2 was used to photolyze HBr molecules, and typically 90% of HBr was decomposed after 1000 pulses.
Q3. What is the effect of tunneling on the decay of cations?
The decomposition of the cations can be caused by their reactions with electrons stored in the matrix as a result of photolysis, and the transfer of the electrons to the positive center occurs via tunneling.
Q4. What is the reason for the bleaching of the S2+ photoluminescence?
The direct neutralization of negative charges with concomitant attachment of the electron to the matrixisolated S2+ ions upon irradiation at 266 nm was suggested as the reason for the bleaching of the S2 + photoluminescence.36
Q5. What is the mechanism of the YHY anions?
They can be formed due to the tunneling of an electron from the Y− center to the neutral Y–HY center originated from the photolysis of HY dimers.
Q6. What is the origin of the 1992-cm1 band?
The 1992-cm−1 band probably originates from the hindered rotation of HArF in an Ar matrix, in analogy with some other HNgY molecules.
Q7. What is the reason for the delay in the formation of the HNgY molecules?
It should be stressed that the delayed formation of the HNgY molecules has been usually promoted by annealing activating diffusion of hydrogen atoms in the matrix, with an important exclusion of IR-decomposed HXeI.
Q8. What are the proposed mechanisms for the global mobility of protons solvated in noble-gas?
The tunneling and light-induced mechanisms for the global mobility of protons solvated in noble-gas solids were proposed by Beyer et al.8,9
Q9. What is the effect of the tunneling of electrons on the YHY an?
As seen in the experiments, the YHY − formation is slower at low temperatures than the decay of the cations, which can be caused by larger distances involved or/and a small concentration of Y–HY centers after photolysis.
Q10. What is the way to explain the tunneling mechanism?
The proposed electron tunneling mechanism should be considered as an alternative to the previously suggested mechanisms based on tunneling-supported or light-induced diffusion of protons in noble-gas lattices.
Q11. Why is the NgHNg ++e neutralization reaction strongly exothermic?
The energetics of this system allows the electron-tunneling process because the NgHNg ++e− neutralization reaction is strongly exothermic due to the large ionization energy of hydrogen 13.5 eV .
Q12. How does the ArHAr + concentration decrease after annealing?
25 Upon annealing at 20 and 33 K the ArHAr + concentration decreases; however, even after the 33-K annealing the cations are very visible in the spectra.
Q13. What is the effect of the light neutralization on the H atoms?
In this model, the mobilization of H atoms resulted from sudden light-induced neutralization of the NgHNg + ion, giving kinetic energy for the light H particle.
Q14. How is the electron tunneling process based on the properties of solidstate photolysis?
It follows from the properties of solidstate photolysis that the negative and positive centers are formed in the vicinity of each other, and the distance is comparable with the lattice parameter 0.5 nm .19
Q15. How can the neutralization reaction promote the formation of HArF?
upon electron transfer from F− to ArHAr + the neutralization reaction can locally introduce some energy to a lattice and hence promote the H+Ar+F reaction, and this mechanism may be operating to some extent.
Q16. What is the effect of the globar radiation on proton decay?
The globar radiation is inefficient in promoting the proton decay so that the blackbody radiation is improbable to do this either.