| Autor: |
Mathew NA; Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA., Rickard MA, Kornau KM, Pakoulev AV, Block SB, Yurs LA, Wright JC |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2009 Sep 10; Vol. 113 (36), pp. 9792-803. |
| DOI: |
10.1021/jp905172p |
| Abstrakt: |
Mixed frequency/time domain, two color triply vibrationally enhanced (TRIVE) four wave mixing (FWM) spectroscopy is used to study the methyl and methylene modes in octane and dotriacontane. The experiments involve scanning different combinations of the two excitation frequencies, the monochromator frequency, and the two time delays between the three excitation pulses while the remaining variables are fixed. Two dimensional spectra of the methyl and methylene stretching region have weak, asymmetrical diagonal- and cross-peaks when the excitation pulses are temporally overlapped. As the time delays change, the spectra change as new peaks appear and their peak intensity and position change. Combined two-dimensional scans of the excitation frequency and time delay show the changes are caused by relaxation of the initially excited populations to other states that are coupled to the methyl and methylene stretching modes. Two dimensional time delay scans show that the coherence dephasing rates are very fast so fully coherent TRIVE FWM pathways involving multiple quantum coherences are not possible without shorter excitation pulses. Similar experiments involving the methyl and methylene bend and stretching modes identify cross-peaks between these modes and population transfer processes that create cross-peaks. The asymmetric methylene stretch/Fermi resonance band is observed to contain unresolved states that couple differently with the symmetric methylene stretching and scissor modes as well as with lower lying quantum states that are fed by population transfer. The TRIVE FWM data show that the multidimensional spectra are dominated by rapid population transfer within the methyl and methylene stretching modes and to lower quantum states that are coupled to the stretching modes. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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