Direct observation of rotational relaxation times by time-resolved infrared spectroscopy

Graener, H.; Seifert, G.; Laubereau, A.

doi:10.1016/0009-2614(90)80134-y

Cited by 88 publications

(64 citation statements)

References 14 publications

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“…This is analogous to orientational relaxation of excited molecules in a liquid, [78][79][80][81] where the excitation polarization diffuses by the orientational motion of the excited oscillators. By probing the excited population in the polarization channels both parallel and perpendicular to the pump polarization, information about orientational motion of the excitations can be obtained.…”

Section: E Polarization Diffusionmentioning

confidence: 99%

“…By probing the excited population in the polarization channels both parallel and perpendicular to the pump polarization, information about orientational motion of the excitations can be obtained. [78][79][80][81] Although the dipoledipole transfer process has a tendency to maintain the polarization via the orientation factor in Eq. ͑8͒, diffusion of the polarization is expected due to the different oscillator orientations ͑see Table II͒.…”

Section: E Polarization Diffusionmentioning

confidence: 99%

“…The anisotropy after excitation, which is defined as the ratio of the maxima of the probe transmission for both polarization channels, 79 aϭ͓ln(T/T 0 )͔ ʈ max /͓ln(T/T 0 )͔ Ќ max , depends on the degree of saturation and thus on the intensity of the pump pulse. In the absence of polarization diffusion for vanishing saturation, a equals 3 ͑see Appendix B͒, but a decreases with increasing saturation.…”

Section: E Polarization Diffusionmentioning

confidence: 99%

“…In the absence of polarization diffusion for vanishing saturation, a equals 3 ͑see Appendix B͒, but a decreases with increasing saturation. 79 We have numerically calculated the time-dependent probe transmission in both polarization channels using the differential equations which describe the excitation of transition dipoles in the sample as a function of time, distance, and orientation, see Appendix B. In these calculations polarization rotation is not taken into account, which means that all excitations keep the same orientation.…”

Section: E Polarization Diffusionmentioning

confidence: 99%

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Direct vibrational energy transfer in zeolites

Brugmans

Bakker

Lagendijk

1996

The Journal of Chemical Physics

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Direct vibrational energy transfer in zeolitesBrugmans, M.J.P.; Bonn, M.; Bakker, H.J.; Lagendijk, A. Published in:Journal of Chemical Physics DOI:10.1063/1.470876 Link to publication Citation for published version (APA):Brugmans, M. J. P., Bonn, M., Bakker, H. J., & Lagendijk, A. (1996). Direct vibrational energy transfer in zeolites. Journal of Chemical Physics, 104, 64-84. DOI: 10.1063/1.470876 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. With two-color picosecond infrared laser spectroscopy the dynamics of O-H and O-D stretch vibrations in zeolites are investigated. Zeolites appear to be good model systems to study transfer of vibrational energy in a solid. For the O-D vibrations, transient spectral holes are burnt in the inhomogeneously broadened absorption bands by saturating the absorption with a strong pump pulse. From the spectral hole widths the homogeneous absorption linewidths are obtained. The excited population lifetimes are determined using a time-resolved pump-probe technique, and in combination with the homogeneous linewidth the pure dephasing time is revealed as well. For high concentrations of O-H oscillators the vibrational stretch excitations are found to diffuse spectrally through the inhomogeneous absorption band. This spectral diffusion process is explained by direct site-to-site transfer of the excitations due to dipole-dipole coupling ͑Förster transfer͒. The dependences of the transient spectral signals on oscillator concentration and the results of one-color polarization resolved experiments confirm this explanation. The spectral transients are satisfactorily described by simulations in which the site-to-site transfer by dipole-dipole coupling is taken into account.

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Section: E Polarization Diffusionmentioning

confidence: 99%

Section: E Polarization Diffusionmentioning

confidence: 99%

Section: E Polarization Diffusionmentioning

confidence: 99%

Section: E Polarization Diffusionmentioning

confidence: 99%

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Direct vibrational energy transfer in zeolites

Brugmans

Bakker

Lagendijk

1996

The Journal of Chemical Physics

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“…The anisotropy decays due to the orientational randomization of excited OD-stretch oscillators, 39 and thus directly reveals the reorientation dynamics of the water molecules. At long time delays, a small residual signal in the absorption difference, associated with heating of the sample by the pump pulse, remains.…”

Section: Methodsmentioning

confidence: 99%

Structure and dynamics of water in nonionic reverse micelles: A combined time-resolved infrared and small angle x-ray scattering study

Loop

Panman

Lotze

et al. 2012

The Journal of Chemical Physics

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We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pumpprobe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H 2 O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surfacewater dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol −1 (11 ± 2 kcal mol −1 ), which is close to the activation energy of the reorientation of water molecules in ice.

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Two‐Dimensional Infrared Spectroscopy Reveals the Structure of an Evans Auxiliary Derivative and Its SnCl₄ Lewis Acid Complex

Messmer

Lippert

Steinwand

et al. 2012

Chemistry A European J

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Determining the structure of reactive intermediates is the key to understanding reaction mechanisms. To access these structures, a method combining structural sensitivity and high time resolution is required. Here ultrafast polarization-dependent two-dimensional infrared (P2D-IR) spectroscopy is shown to be an excellent complement to commonly used methods such as one-dimensional IR and multidimensional NMR spectroscopy for investigating intermediates. P2D-IR spectroscopy allows structure determination by measuring the angles between vibrational transition dipole moments. The high time resolution makes P2D-IR spectroscopy an attractive method for structure determination in the presence of fast exchange and for short-lived intermediates. The ubiquity of vibrations in molecules ensures broad applicability of the method, particularly in cases in which NMR spectroscopy is challenging due to a low density of active nuclei. Here we illustrate the strengths of P2D-IR by determining the conformation of a Diels-Alder dienophile that carries the Evans auxiliary and its conformational change induced by the complexation with the Lewis acid SnCl(4), which is a catalyst for stereoselective Diels-Alder reactions. We show that P2D-IR in combination with DFT computations can discriminate between the various conformers of the free dienophile N-crotonyloxazolidinone that have been debated before, proving antiperiplanar orientation of the carbonyl groups and s-cis conformation of the crotonyl moiety. P2D-IR unequivocally identifies the coordination and conformation in the catalyst-substrate complex with SnCl(4), even in the presence of exchange that is fast on the NMR time scale. It resolves a chelate with the carbonyl orientation flipped to synperiplanar and s-cis crotonyl configuration as the main species. This work sets the stage for future studies of other catalyst-substrate complexes and intermediates using a combination of P2D-IR spectroscopy and DFT computations.

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Direct observation of rotational relaxation times by time-resolved infrared spectroscopy

Cited by 88 publications

References 14 publications

Direct vibrational energy transfer in zeolites

Direct vibrational energy transfer in zeolites

Structure and dynamics of water in nonionic reverse micelles: A combined time-resolved infrared and small angle x-ray scattering study

Two‐Dimensional Infrared Spectroscopy Reveals the Structure of an Evans Auxiliary Derivative and Its SnCl₄ Lewis Acid Complex

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Direct observation of rotational relaxation times by time-resolved infrared spectroscopy

Cited by 88 publications

References 14 publications

Direct vibrational energy transfer in zeolites

Direct vibrational energy transfer in zeolites

Structure and dynamics of water in nonionic reverse micelles: A combined time-resolved infrared and small angle x-ray scattering study

Two‐Dimensional Infrared Spectroscopy Reveals the Structure of an Evans Auxiliary Derivative and Its SnCl4 Lewis Acid Complex

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Two‐Dimensional Infrared Spectroscopy Reveals the Structure of an Evans Auxiliary Derivative and Its SnCl₄ Lewis Acid Complex