Electronic Resource
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
114 (2001), S. 10288-10293
ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We have investigated the photodissociation spectroscopy of the Mg+–acetaldehyde bimolecular complex over the spectral range 220–400 nm. We find evidence for four distinct absorption bands in the near ultraviolet that correlate with Mg+-based and acetaldehyde-based transitions. Our results suggest that the Mg+-centered 3pπ(A″)←3sσ(A′) and acetaldehyde-centered π*(A″)←n(A′) transitions are mixed, and result in significant vibrational excitation in the complex leading to broad and unresolved absorption bands. In contrast, the predominantly Mg+-based excitation bands, assigned as 3pπ(A′)←3sσ(A′) and 3pσ(A′)←3sσ(A′), each show prominent vibrational progressions identified with intermolecular wagging modes of the complex. These intermolecular wag progressions are short and anharmonic indicating low barriers to isomerization. In the 3pσ(A′)←3sσ(A′) band several higher frequency vibrational modes are also active and have been assigned to the Mg–OCHCH3 intermolecular stretch, a CCO deformation mode, and the C–O stretch. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1374579
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