The vibrational and rotational relaxation of iodine in solution by resonance Raman lineshape measurement

Battaglia, Maurice R.; Madden, Paul A.

doi:10.1080/00268977800102621

Cited by 46 publications

(21 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This value is slightly greater than z2R = 2-3 ps obtained at room temperature for the looser 12 CC14 complex [40].…”

Section: Estimation Of the Vibrational Relaxation Of Iodine In Benzencontrasting

confidence: 42%

“…Indeed, the orientational correlation time T2R obtained from Raman measurements on neat liquid benzene is about 2.52 ps [-42]. This value is close to the value z2R = 2"3 ps obtained for iodine [40]. It seems also unlikely that the uncertainties in the evaluation of the vibrational contribution associated with the iodine stretching vibration could explain the apparent failure of the crude approximation.…”

Section: Line Shape Analysismentioning

confidence: 78%

“…As a result, the observed shoulder might be attributed to the 2 ~ 3 transition while on the contrary the fundamental and 1 ~ 2 transitions, very close in frequency, certainly overlap and are not resolved. Close to resonance, at argon ion laser frequency, these considerations do not apply, in particular the ratio of the intensity of the hot bands do not obey a simple Boltzmann distribution law [40]. This might explain the observation of more symmetrical profiles.…”

Section: Estimation Of the Vibrational Relaxation Of Iodine In Benzenmentioning

confidence: 96%

See 2 more Smart Citations

Far infrared study of the benzene-iodine complex

Lascombe

Besnard

1986

Molecular Physics

View full text Add to dashboard Cite

A theory of the lineshape of the infrared spectra of weak charge transfer complexes which emphasizes only the electrostatic interactions--namely quadrupole-induced dipole interactions--between the acceptor and donor molecules is presented and applied to the iodine-benzene complex in dilute solutions.For this complex, it is predicted that the I.R. spectra result from a weighted sum of an induced low frequency profile centred at about 100cm -1, with the profile centred at the iodine stretching frequency (205 cm-l) resulting from the convolution operation of an induced profile with the vibrational profile associated with the iodine molecule. These induced profiles are the same if the rotational motions of benzene and iodine are identical.The experimental data are analysed within the framework of this theory using for this purpose the iodine vibrational profile estimated from Raman measurements and Mori's three-variable profiles for the induced ones. The best agreement is obtained using two different induced profiles for the high and low frequency spectra, the correlation times of which differ by about an order of magnitude; the shorter one being associated with the very low frequency I.R. profile. This result might suggest that the rotational behaviour of the benzene and iodine molecules are very different in contradiction with Raman observations. It is thus argued that these spectra reflect different temporal aspects of the very complex auto-correlation function (a.c.f.) of the induced dipole moment of the system.The broad band is related to the very fast fluctuations of the induced dipole moment due to local motions of the iodine-benzene cage and provides information on the short time behaviour of the a.c.f. This is seen on the corresponding correlation function which decreases very rapidly with an associated correlation time close to the one observed for collision-induced spectra of liquids composed of non-polar molecules. On the contrary, the correlation function associated with the high frequency vi_ x induced profile decreases more slowly; the value of its correlation time which is of the order of magnitude of the one obtained from dielectric experiments is slightly lower than the rotational correlation times of iodine and benzene molecules. This profile is influenced by the long-time behaviour of the induced dipole moment and depends upon both the orientational motions and the mutual diffusion of the molecules. Hence it might contain information on the life time of the complex.Finally, the theoretical zero and second moments of the spectra associated with the low frequency induced spectral density are calculated. The value which is found for the former is in good agreement with the corresponding experimental one. However it is important to note that the experimental t Author to whom correspondence should be addressed. Downloaded by [New York University] at 07:22 20 June 2015 574 J. Lascombe and M. Besnarddetermination of this quantity is subject to considerable error. The experimental second moment, which is ...

show abstract

“…This value is slightly greater than z2R = 2-3 ps obtained at room temperature for the looser 12 CC14 complex [40].…”

Section: Estimation Of the Vibrational Relaxation Of Iodine In Benzencontrasting

confidence: 42%

Section: Line Shape Analysismentioning

confidence: 78%

Section: Estimation Of the Vibrational Relaxation Of Iodine In Benzenmentioning

confidence: 96%

See 1 more Smart Citation

Far infrared study of the benzene-iodine complex

Lascombe

Besnard

1986

Molecular Physics

View full text Add to dashboard Cite

show abstract

“…This is somewhat surprising because in liquids the frequency time correlation function is expected to be short and in the motionally narrowed limit. Overtone transition studies that have been attempted earlier 12,13 have reported similar sub-quadratic quantum number dependence, although these observations involved a considerable amount of uncertainty because of low signal-to-noise factors of the bandwidth measurements.…”

Section: Introductionmentioning

confidence: 98%

Dynamic solvent effects on the vibrational overtone dephasing in molecular liquids: Subquadratic quantum number dependence

Gayathri

Bhattacharyya

Bagchi

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inSolvent dependence of OH bend vibrational relaxation of monomeric water molecules in liquids Temperature-dependent vibrational dephasing: Comparison of liquid and glassy solvents using frequencyselected vibrational echoes A theoretical study of vibrational dephasing of molecular vibrations in liquids is presented with an aim to understand the experimentally observed sub-quadratic quantum number (n) dependence of the vibrational dephasing rate, in systems like CH 3 I and CHCl 3 and their deuterated analogues. The analysis is based on Oxtoby's theory of vibrational dephasing but with a detailed microscopic description of the frequency dependent frictional forces on the vibrational mode. The friction on the normal coordinate in liquids is found to have a pronounced biphasic behavior with a dominant Gaussian initial component followed by a slow exponential-like relaxation. While the exponential relaxation usually assumed in Kubo's stochastic theory leads to a quadratic n dependence of the dephasing rate, the biphasic friction is shown to give rise to the sub-quadratic n dependence. As the biphasic frictional response is expected to be a generic feature of the friction on any vibrational coordinate in dense liquids, the sub-quadratic quantum number dependence is predicted to be common to most ultrafast overtone dephasing. In addition, the calculated rates ͑without any adjustable parameter͒, are found to be in good agreement with the experimental results for the C-I stretching mode in liquid CH 3 I and for the C-H stretching in liquid CHCl 3 .

show abstract

“…If the r s 2 terms become important, the 0→1 and the 1→2 transitions will both be equally broadened. 36,41,42 In this case, a change in r induces a difference between the (v OD ϭ 0) and (v OD ϭ 1) hydrogen-bond potentials, that is equal to the difference between the (v OD ϭ 1) and (v OD ϭ 2) potentials: The hole and the hot band will both have the same, non-zero width. It is only when third-or higher-order terms become significant that the width of the 0→1 will be different from that of the 1→2.…”

Section: B Coupling Mechanism For Hydrogen-bond Induced Dephasingmentioning

confidence: 99%

Infrared picosecond transient hole-burning studies of the effect of hydrogen bonds on the vibrational line shape

Bonn

Brugmans

Kleyn

et al. 1996

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inInfrared spectroscopy of OH stretching vibrations of hydrogenbonded tropolone(H2O) n (n=1-3) and tropolone (CH3OH) n (n=1 and 2) clusters High resolution Fourier transform stimulated emission and molecular beam holeburning spectroscopy with picosecond excitation sources: Theoretical and experimental results J. Chem. Phys. 96, 179 (1992); 10.1063/1.462498Line shape of transient burned hole at the dephasing induced by slow stochastic frequency modulation AIP Conf.With infrared transient hole-burning spectroscopy we have investigated the influence of OD•••X hydrogen bonds on the vibrational line shape of O-D stretch vibrations in acid zeolites. The effect of hydrogen bonding on the line shape depends critically on the type of hydrogen bond. For hydrogen bonding in a rigid structure, the hydrogen bond determines the inhomogeneous linewidth, but the homogeneous linewidth is determined by coupling to a ϳ200 cm Ϫ1 lattice mode as concluded from the temperature dependence of the dephasing rate. When the hydrogen bond is formed with an adsorbing molecule, the coupling between the high-frequency O-D stretch vibration and the low-frequency OD•••X hydrogen-bond stretching mode does determine the homogeneous linewidth. The difference between the two systems can be explained by the different hydrogen-bond potentials. Variation of the adsorbate provides a means of obtaining conclusive information on the coupling mechanism between the high-frequency O-D stretching mode and the low-frequency OD•••X hydrogen-bond stretching mode.

show abstract

The vibrational and rotational relaxation of iodine in solution by resonance Raman lineshape measurement

Cited by 46 publications

References 19 publications

Far infrared study of the benzene-iodine complex

Far infrared study of the benzene-iodine complex

Dynamic solvent effects on the vibrational overtone dephasing in molecular liquids: Subquadratic quantum number dependence

Infrared picosecond transient hole-burning studies of the effect of hydrogen bonds on the vibrational line shape

Contact Info

Product

Resources

About