Vibrational Relaxation of Liquid Chloroform

Graener, H.; Zürl, R.; Hofmann, M.

doi:10.1021/jp9624212

Cited by 82 publications

(97 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For large molecules in solution, the collision rates are on the order of 10 12 s Ϫ1 , which is close to the time scale of IVR, and this brings about complex evolutions of vibrational population. 7 Recently the evolutions of vibrational population of many fundamentals were studied in detail for small molecules and showed mode-specific intermolecular vibrational energy transfer, [8][9][10] which indicates that the two steps are not temporally distinct. However, the time scales of IVR and IET are not clear for large molecules in solution due to lack of detailed studies.…”

Section: Intramolecular Vibrational Energy Redistribution and Intermomentioning

confidence: 99%

Intramolecular vibrational energy redistribution and intermolecular energy transfer in the (d, d) excited state of nickel octaethylporphyrin

Mizutani

Uesugi

Kitagawa

1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

The formation of a vibrationally excited photoproduct of nickel octaethylporphyrin (NiOEP) upon (π, π*) excitation and its subsequent vibrational energy relaxation were monitored by picosecond time-resolved resonance Raman spectroscopy. Stokes Raman bands due to the photoproduct instantaneously appeared upon the photoexcitation. Their intensities decayed with a time constant of ∼300 ps, which indicates electronic relaxation from the (d, d) excited state (B1g) to the ground state (A1g), being consistent with the results of transient absorption measurements by Holten and co-workers [D. Kim, C. Kirmaier, and D. Holten, Chem. Phys. 75, 305 (1983); J. Rodriguez and D. Holten, J. Chem. Phys. 91, 3525 (1989)]. The Raman frequencies of NiOEP in the (d, d) excited state are shifted to lower frequencies compared to those of the ground state species, and it is reasonably interpreted by the core size expansion of the macrocycle by 0.05 Å upon the electron promotion from the dz2 to the dx2−y2 orbital. Anti-Stokes ν4 intensity in the vibrationally excited (d, d) state of NiOEP appeared promptly and decayed with time constants of 11±2 and 330±40 ps. The former is ascribed to vibrational relaxation, while the latter corresponds to the electronic relaxation from the (d, d) excited state to the electronic ground state. In contrast, the rise of anti-Stokes ν7 intensity was not instantaneous, but delayed by 2.6±0.5 ps, which indicates that intramolecular vibrational energy redistribution has not been completed in subpicosecond time regime. The peak position of the ν4 band shifted by nearly 5 cm−1 between 0 and 50 ps. The time constant for the shift of the ν4 band was 9.2±1.3 ps, which was close to that for the fast component of intensity decay of anti-Stokes bands. The ν4 band became narrower and symmetric as the delay time increases. These can be ascribed to intramolecular anharmonic coupling of the ν4 mode with the low frequency modes. The intra- and intermolecular vibrational energy relaxation in the metal excited state will be discussed.

show abstract

Section: Intramolecular Vibrational Energy Redistribution and Intermomentioning

confidence: 99%

Intramolecular vibrational energy redistribution and intermolecular energy transfer in the (d, d) excited state of nickel octaethylporphyrin

Mizutani

Uesugi

Kitagawa

1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…This picture recovers the limiting mechanisms of state-specific IVR, where only a few states are in the first tier, and of statistical IVR, where a large number of states compose the first tier. The vibrational relaxation process is even more complicated in solution, [27][28][29][30][31][32][33][34][35][36][37][38][39][40] where intermolecular energy transfer ͑IET͒ to the solvent is important. IET depends on the internal vibrational modes of the solute, as well as the surrounding environment, since some modes transfer energy to the solvent more effectively than others.…”

Section: Introductionmentioning

confidence: 99%

Vibrational relaxation of CH2I2 in solution: Excitation level dependence

Elles

Bingemann

Heckscher

et al. 2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

Transient electronic absorption monitors the flow of vibrational energy in methylene iodide (CH 2 I 2 ) following excitation of five C-H stretch and stretch-bend modes ranging in energy from 3000 to 9000 cm Ϫ1 . Intramolecular vibrational relaxation ͑IVR͒ occurs through a mechanism that is predominantly state-specific at the C-H stretch fundamental but closer to the statistical limit at higher excitation levels. The IVR times change with the excitation energy between the fundamental and first C-H stretch overtone but are constant above the overtone. The intermolecular energy transfer ͑IET͒ times depend only weakly on the initial excitation level. Both the IVR and the IET times depend on the solvent ͓CCl 4 , CDCl 3 , C 6 D 6 , C 6 H 6 , or (CD 3 ) 2 CO] and its interaction strength, yet there is no energy level dependence of the solvent influence.

show abstract

“…24 Recently, Graener and co-workers used a 50 Hz Nd : YLF system with 1.5 ps resolution to study VER in dichloromethane 25 (CH 2 Cl 2 ) and chloroform 26 (CHCl 3 ) after C-H stretch excitation. The latter work 26 is especially notable for being the first where every one of the vibrations of a particular polyatomic molecule was monitored during a VER process. Recently, our group has developed an experimental system based on a Ti : sapphire laser, which provides 1 ps time resolution and unprecedented sensitivity.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast infrared-Raman studies of vibrational energy redistribution in polyatomic liquids

Deàk

Iwaki

Rhea

et al. 2000

J. Raman Spectrosc.

View full text Add to dashboard Cite

Vibrational energy relaxation and vibrational cooling of polyatomic liquids were studied with the ultrafast infrared-Raman (IR-Raman) technique. In the IR-Raman technique, a type of two-dimensional vibrational spectroscopy, a vibrational transition is pumped with a mid-infrared pulse and the instantaneous populations of all Raman-active transitions are simultaneously probed via incoherent anti-Stokes Raman scattering of a time-delayed visible pulse. The theoretical framework for these measurements, including force-force correlation function methods and perturbative techniques, is reviewed. Experimental aspects of the IR-Raman technique are discussed, including laser instrumentation, experimental set-up, the nature of the pumping and probing processes, detection sensitivity and optical background, and the interpretation of results including spectroscopic artifacts. Then examples are provided from recent research by our group, focusing on timely problems such as the pseudo-vibrational cascade, the dynamics of doorway vibrations, dynamics of overtones with Fermi resonance, multiple vibrational excitations via combination band pumping and spectral evolution in associated liquids.

show abstract

Vibrational Relaxation of Liquid Chloroform

Cited by 82 publications

References 20 publications

Intramolecular vibrational energy redistribution and intermolecular energy transfer in the (d, d) excited state of nickel octaethylporphyrin

Intramolecular vibrational energy redistribution and intermolecular energy transfer in the (d, d) excited state of nickel octaethylporphyrin

Vibrational relaxation of CH2I2 in solution: Excitation level dependence

Ultrafast infrared-Raman studies of vibrational energy redistribution in polyatomic liquids

Contact Info

Product

Resources

About