Photochemical processes on chloromethyl formate and vinyl formate in low-temperature matrices: infrared spectra and ab initio calculations on chloromethanol and vinyl alcohol

.. ClH/sub 2/COH + CO; H/sub 2/CCHOCHO ..-->.. H/sub 2/CCHOH + CO. (ii) ClH/sub 2/COCHO ..-->.. H/sub 2/CO + HCl + CO; H/sub 2/CCHOCHO ..-->.. CH/sub 3/CHO + CO. There is a well-established wavelength dependence influencing the product ratios in these photochemical processes. Decomposition due to irradiation at wavelengths near 250 nm prefers channel i, where the formic acid esters decompose to the corresponding alcoholic species, chloromethanol (a new compound), and vinyl alcohol. On the other hand, at shorter wavelengths, channel ii dominates. Neither chloromethanol nor vinyl alcohol were observed to decompose at wavelengths above 200 nm. The photoprocesses of vinyl formate were also studied in NO-doped Ar matrices as well as in solid Xe in order to get information concerning the mechanisms of photochemical decomposition of formic acid esters. The assignment of the vibrational spectra is based on ab inito calculations performed at the Hartree-Fock 6-31G** level for chloromethanol and at the MP2/6-31G** level for vinyl alcohol. A detailed vibrational analysis is given formore » chloromethanol, chloromethanol-O-d, and vinyl alcohol.« less -->
ISSN: 1541-5740
0022-3654
DOI: 10.1021/j100317a024
Přístupová URL adresa: https://explore.openaire.eu/search/publication?articleId=doi_________::203fe85b80dcf8ad3e2d8f921d30e42b
https://doi.org/10.1021/j100317a024
Přírůstkové číslo: edsair.doi...........203fe85b80dcf8ad3e2d8f921d30e42b
Autor: Juhani Murto, Henrik Kunttu, Markku Räsänen, Martti Dahlqvist
Rok vydání: 1988
Předmět:
Zdroj: The Journal of Physical Chemistry. 92:1495-1502
ISSN: 1541-5740
0022-3654
DOI: 10.1021/j100317a024
Popis: The UV decomposition of chloromethyl formate and vinyl formate has been studied in low-temperature noble gas matrices at wavelengths between 200 and 260 nm. Two distinct channels in cage photolysis were observed: (i) ClH/sub 2/COCHO ..-->.. ClH/sub 2/COH + CO; H/sub 2/CCHOCHO ..-->.. H/sub 2/CCHOH + CO. (ii) ClH/sub 2/COCHO ..-->.. H/sub 2/CO + HCl + CO; H/sub 2/CCHOCHO ..-->.. CH/sub 3/CHO + CO. There is a well-established wavelength dependence influencing the product ratios in these photochemical processes. Decomposition due to irradiation at wavelengths near 250 nm prefers channel i, where the formic acid esters decompose to the corresponding alcoholic species, chloromethanol (a new compound), and vinyl alcohol. On the other hand, at shorter wavelengths, channel ii dominates. Neither chloromethanol nor vinyl alcohol were observed to decompose at wavelengths above 200 nm. The photoprocesses of vinyl formate were also studied in NO-doped Ar matrices as well as in solid Xe in order to get information concerning the mechanisms of photochemical decomposition of formic acid esters. The assignment of the vibrational spectra is based on ab inito calculations performed at the Hartree-Fock 6-31G** level for chloromethanol and at the MP2/6-31G** level for vinyl alcohol. A detailed vibrational analysis is given formore » chloromethanol, chloromethanol-O-d, and vinyl alcohol.« less
Databáze: OpenAIRE
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