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Integrated and dispersed photon echo studies of nitrile stretching vibration of 4-cyanophenol in methanol

Authors
Ha, Jeong-HyonLee, Kyung-KooPark, Kwang-HeeChoi, Jun-HoJeon, Seung-JoonCho, Minhaeng
Issue Date
28-May-2009
Publisher
AMER INST PHYSICS
Keywords
excited states; infrared spectra; intramolecular mechanics; organic compounds; spectral line breadth; vibrational states
Citation
JOURNAL OF CHEMICAL PHYSICS, v.130, no.20
Indexed
SCIE
SCOPUS
Journal Title
JOURNAL OF CHEMICAL PHYSICS
Volume
130
Number
20
URI
https://scholar.korea.ac.kr/handle/2021.sw.korea/120023
DOI
10.1063/1.3140402
ISSN
0021-9606
Abstract
By means of integrated and dispersed IR photon echo measurement methods, the vibrational dynamics of C-N stretch modes in 4-cyanophenol and 4-cyanophenoxide in methanol is investigated. The vibrational frequency-frequency correlation function (FFCF) is retrieved from the integrated photon echo signals by assuming that the FFCF is described by two exponential functions with about 400 fs and a few picosecond components. The excited state lifetimes of the C-N stretch modes of neutral and anionic 4-cyanophenols are 1.45 and 0.91 ps, respectively, and the overtone anharmonic frequency shifts are 25 and 28 cm(-1). At short waiting times, a notable underdamped oscillation, which is attributed to a low-frequency intramolecular vibration coupled to the CN stretch, in the integrated and dispersed vibrational echo as well as transient grating signals was observed. The spectral bandwidths of IR absorption and dispersed vibrational echo spectra of the 4-cyanophenoxide are significantly larger than those of its neutral form, indicating that the strong interaction between phenoxide and methanol causes large frequency fluctuation and rapid population relaxation. The resonance effects in a paradisubstituted aromatic compound would be of interest in understanding the conjugation effects and their influences on chemical reactivity of various aromatic compounds in organic solvents.
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