Intramolecular vibrational dynamics in free polyatomic molecules with CâO chromophore bond excited by resonant femtosecond IR laser radiation.
J Phys Chem A
; 118(6): 955-64, 2014 Feb 13.
Article
em En
| MEDLINE
| ID: mdl-24467228
ABSTRACT
In nine polyatomic molecules, we have studied the intramolecular redistribution of vibrational energy from chromophore CâO group excited by a resonant femtosecond IR laser radiation at a wavelength of â¼5 µm. All experiments have been performed in the gas phase using the IR-IR pump-probe technique in combination with the spectral analysis of the probe radiation. For molecules with one CâO end group, characteristic times of intramolecular vibrational redistribution (IVR) lie in the range between 2.4 and 20 ps and correlate with the density of four-frequency Fermi resonances. The IVR times in metal carbonyl molecules are anomalously long, being â¼1.0 ns for Fe(CO)5 and â¼1.5 ns for Cr(CO)6. In the CH3(CâO)OC2H5 and H2CCH(CâO)OC2H5 molecules, it has been observed that there are two characteristic IVR times, which differ by an order of magnitude from each other; this was interpreted in terms of the developed model of "accumulating states". For the ICF2COF molecule, it has been revealed that the IVR time decreases with increasing level of the vibrational excitation of the CâO bond of the molecule.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Tipo de estudo:
Prognostic_studies
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2014
Tipo de documento:
Article
País de afiliação:
Federação Russa