期刊
FARADAY DISCUSSIONS
卷 163, 期 -, 页码 33-57出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3fd20160k
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资金
- Department of Energy [DEFG0287ER13671]
- Petroleum Research Fund [50650-ND6]
- Air Force Office of Scientific Research [FA9550-09-1-0330]
- National Science Foundation [1126380]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1126380] Funding Source: National Science Foundation
Chirped-Pulse millimetre-Wave (CPmmW) rotational spectroscopy provides a new class of information about photolysis transition state(s). Measured intensities in rotational spectra determine species-isomer-vibrational populations, provided that the rotational populations can be thermalized. The formation and detection of S-0 vinylidene is discussed in the limits of low and high initial rotational excitation. CPmmW spectra of 193 nm photolysis of vinyl cyanide (acrylonitrile) contain J = 0-1 transitions in more than 20 vibrational levels of HCN and HNC, but no transitions in vinylidene or highly excited local-bender vibrational levels of acetylene. Reasons for the non-observation of the vinylidene co-product of HCN are discussed.
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