Intramolecular vibrational dynamics in bis(trifluoromethyl)keten excited by resonant femtosecond IR radiation

Чекалин, С. В.; Компанец, В. О.; Laptev, V. B.; Pigulsky, S. V.; Макаров, А. А.; Ryabov, E. A.

doi:10.1016/j.cplett.2011.07.029

Cited by 20 publications

(27 citation statements)

References 19 publications

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“…The experiments confirmed a selective excitation of the resonant mode ν1 up to vibrational level v = 5, which was previously registered by another way [2]. As the level of vibrational excitation of the resonant mode grows up the exponential decrease of the ΔOD signal was observed with characteristic times from W = 6 ps for the transitions 0 1 and 1 2 to W = 3.5 ps for the transitions 4 5 and 5 6.…”

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confidence: 66%

Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

et al. 2016

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Abstract. Intramolecular dynamics of the vibrational levels (up to v = 5) of the ν1 mode in (CF3)2CCO molecule, induced via multiphoton selective excitation of this mode by resonant femtosecond IR radiation, was studied. The times of intramolecular vibrational energy redistribution (IVR) of each vibrational level v to the remaining modes of the molecule were measured. In accordance with the theory predictions the decrease of IVR time with increasing v is observed. A sharp reduction of the IVR time (up to 1 ps) at a wavelength of 2130 cm 1 of transition v=3 o v=4 was found. It was shown that with a negative chirp of a femtosecond radiation pulse the population of high-lying vibrational levels of ν1 modes significantly increases.At a multiphoton excitation of selected vibrational modes in the molecule an implementation of photochemical bond-selective processes (or group of bonds) is possible. However, this possibility is limited due to effect of rapid intramolecular energy redistribution (IVR) from the excited mode to other vibrations of the molecule [1]. It is therefore important to study the process of IVR for different vibrational levels of the excited molecule. The aim of this work was to study vibrational dynamics in bis (trifluoromethyl) molecule (CF3)2CCO, resulting from multiphoton excitation of the ν1 =2194 cm 1 mode of the C=C=O bond vibration by resonance IR femtosecond radiation.In the experiments the IR pump-probe method with a spectral analysis of the probing radiation was used. For this purpose the new IR detector, namely high-sensitive and lownoise linear array on the basis of CdHgTe, developed with the participation of the authors, was employed for the first time. Measurements were carried out in the gas phase at low pressure, which made it possible to completely avoid the influence of intermolecular interaction. The duration of the pump and probe pulses was 120 fs with a spectral width of ~230 cm 1 . The spectra of induced transmission/absorption ΔOD depending on the delay

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confidence: 66%

Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

et al. 2016

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“…Then, the spectra have rather long "tails". In total, the spectrum at Δt = 0.8 ps corresponds to that obtained in our previous work 13 by the point-by-point method. At the same time, the new registration system made it possible to observe the dynamics of the "tail" of the Δk OD spectrum.…”

Section: ■ Resultsmentioning

confidence: 81%

“…However, this value can only be used if the bath states are weakly mixed, which is unlikely. The measured value of (2πcτ IVR ) −1 is approximately 1 cm −1 (∼5 ps 13 ), so the golden rule may be valid even in the third unlikely case. The objective of this work is to study particular features of the dynamics of excited vibrational levels of the mode ν 1 = 2194 cm −1 in bis(trifluoromethyl)keten ((CF 3 ) 2 CCO) molecules that proceeds after its selective excitation by resonant femtosecond IR radiation.…”

Section: ■ Introductionmentioning

confidence: 88%

“…In our opinion, this was caused by a low intensity of the induced absorption signal from vibrationally excited molecules and, correspondingly, was due to high errors in determining the characteristic damping time of the signal. 13 Development of high-sensitivity and low-noise IR detectors based on a CdHgTe linear array opened up new opportunities for measuring the induced optical density with a high accuracy.…”

Section: ■ Introductionmentioning

confidence: 99%

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IVR Dynamics of Vibrational Levels of the ν₁ Mode in (CF₃)₂C═C═O Molecules Excited by Resonant IR Femtosecond Radiation

et al. 2019

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The intramolecular dynamics of vibrational levels (up to v = 5) of the ν1 mode in the (CF3)2CCO molecule that is induced by a multiphoton selective excitation of this mode by resonant femtosecond IR radiation has been studied. The times of intramolecular vibrational energy redistribution (IVR) from each vibrational level to remaining molecular modes have been determined. In accordance with theoretical predictions, a decrease in the IVR time with increasing quantum number v has been observed for the first time. A sharp decrease in the IVR time (down to 1.5 ps) at a wavelength of 2129 cm–1, corresponding to the v = 3 → v = 4 vibrational transition, is revealed. It has been shown that, with a negative chirp of a femtosecond radiation pulse, the population of high-lying vibrational levels of the ν1 mode increases significantly.

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“…In the simplest variant, which we used in this work, the pump and probe radiation beams were reunited at a small angle to each other; therefore, the probe region was relatively small, 0.046 cm. 26 Nevertheless, this proved to be quite sufficient to measure Δk OD signals from all the examined molecules. The passage to a collinear geometry makes it possible to increase the sensitivity of the method almost by an order of magnitude.…”

Section: Discussionmentioning

confidence: 99%

Intramolecular Vibrational Dynamics in Free Polyatomic Molecules with C═O Chromophore Bond Excited by Resonant Femtosecond IR Laser Radiation

et al. 2014

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In nine polyatomic molecules, we have studied the intramolecular redistribution of vibrational energy from chromophore C═O group excited by a resonant femtosecond IR laser radiation at a wavelength of ∼5 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 C═O 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 ∼1.0 ns for Fe(CO)5 and ∼1.5 ns for Cr(CO)6. In the CH3(C═O)OC2H5 and H2CCH(C═O)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 C═O bond of the molecule.

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Intramolecular vibrational dynamics in bis(trifluoromethyl)keten excited by resonant femtosecond IR radiation

Cited by 20 publications

References 19 publications

Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

IVR Dynamics of Vibrational Levels of the ν₁ Mode in (CF₃)₂C═C═O Molecules Excited by Resonant IR Femtosecond Radiation

Intramolecular Vibrational Dynamics in Free Polyatomic Molecules with C═O Chromophore Bond Excited by Resonant Femtosecond IR Laser Radiation

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Intramolecular vibrational dynamics in bis(trifluoromethyl)keten excited by resonant femtosecond IR radiation

Cited by 20 publications

References 19 publications

Intramolecular vibrational dynamics of ν1mode in (CF3)2C=C=O molecule induced by resonant IR femtosecond radiation

Intramolecular vibrational dynamics of ν1mode in (CF3)2C=C=O molecule induced by resonant IR femtosecond radiation

IVR Dynamics of Vibrational Levels of the ν1 Mode in (CF3)2C═C═O Molecules Excited by Resonant IR Femtosecond Radiation

Intramolecular Vibrational Dynamics in Free Polyatomic Molecules with C═O Chromophore Bond Excited by Resonant Femtosecond IR Laser Radiation

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Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

Intramolecular vibrational dynamics of ν₁mode in (CF₃)₂C=C=O molecule induced by resonant IR femtosecond radiation

IVR Dynamics of Vibrational Levels of the ν₁ Mode in (CF₃)₂C═C═O Molecules Excited by Resonant IR Femtosecond Radiation