Evidence for Cooperative Vibrational Relaxation of the NH-, OH-, and OD-Stretching Modes in Hydrogen-Bonded Liquids Using Infrared Pump-Probe Spectroscopy

Shaw, Daniel J.; Panman, Matthijs R.; Woutersen, Sander

doi:10.1103/physrevlett.103.227401

Cited by 13 publications

(16 citation statements)

References 16 publications

(18 reference statements)

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“…Interestingly, experiments outside a cavity [22] have shown that vibrational relaxation rates in hydrogenbonded liquids (X H/X D mixture) demonstrate similar sensitive dependence on isotope concentration as we have found inside a cavity in Fig. 4b.…”

Section: Rabi Splitting Dependencesupporting

confidence: 81%

Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations

Li,

Nitzan,

Subotnik

2021

Preprint

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For a small fraction of hot CO 2 molecules immersed in a liquid-phase CO 2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C O asymmetric stretch of CO 2 molecules and a cavity mode accelerates hotmolecule relaxation. The physical mechanism underlying this acceleration is the fact that polaritons, especially the lower polariton, can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates (i) resonantly depend on the cavity mode detuning, (ii) cooperatively depend on molecular concentration or Rabi splitting, and (iii) collectively scale with the number of hot molecules, which is similar to Dicke's superradiance. For larger cavity volumes, due to a balance between this superradiant-like behavior and a smaller light-matter coupling, the total VSC effect on relaxation rates can scale slower than 1/N , and the average VSC effect per molecule can remain meaningful for up to N ∼ 10 4 molecules forming VSC. Moreover, we find that the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than equally distributing it to all thermal molecules. Finally, we highlight the similarities of parameter dependence between the current finding with VSC catalysis observed in Fabry-Pérot microcavities.

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Section: Rabi Splitting Dependencesupporting

confidence: 81%

Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations

Li,

Nitzan,

Subotnik

2021

Preprint

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“…Ethanol-OD in ethanol-OH has an OD-stretch T 1 of 800 fs (Ref. 44) and methanol-OD in methanol-OH of 500 fs, 45 both of which agree well with the 810 fs for the fast component that we observe. To confirm our hypothesis that the fast component is due to Igepal, we also measured the transient response of the OD-stretch vibration in neat Igepal, which reveals a similar fast component of 1.2 ps.…”

Section: Resultssupporting

confidence: 77%

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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“…The dependence on the isotopic dilution of the fast relaxation time, instead, is still debated. 37,38,42 4 Liquid water…”

Section: Discussionmentioning

confidence: 99%

“…The dynamics of hydrogen bonded liquids is usually investigated by labeling the highest frequency vibrational mode, 3 namely: the OH stretching mode. For the sake of comparison with experimental results 37,38 we considered 100% fully deuterated methanol, CH 3 OD and the excitation of the OD stretching mode.…”

Section: Probing the System Relaxationmentioning

confidence: 99%

Simulating Energy Relaxation in Pump–Probe Vibrational Spectroscopy of Hydrogen-Bonded Liquids

Dettori

Ceriotti

Hunger

et al. 2017

J. Chem. Theory Comput.

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We introduce a non-equilibrium molecular dynamics simulation approach, based on the generalized Langevin equation, to study vibrational energy relaxation in pump-probe spectroscopy. A colored noise thermostat is used to selectively excite a set of vibrational modes, leaving the other modes nearly unperturbed, to mimic the effect of a monochromatic laser pump. Energy relaxation is probed by analyzing the evolution of the system after excitation in the microcanonical ensemble, thus providing direct information about the energy redistribution paths at the molecular level and their time scale. The method is applied to hydrogen bonded 1 molecular liquids, specifically deuterated methanol and water, providing a robust picture of energy relaxation at the molecular scale.

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Evidence for Cooperative Vibrational Relaxation of the NH-, OH-, and OD-Stretching Modes in Hydrogen-Bonded Liquids Using Infrared Pump-Probe Spectroscopy

Abstract: Evidence for cooperative vibrational relaxation of the NH-, OH-, and OD-stretching modes in hydrogen-bonded liquids using infrared pump-probe spectroscopy Shaw, J.D.; Panman, M.R.; Woutersen, S.

Cited by 13 publications

References 16 publications

Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations

Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations

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

Simulating Energy Relaxation in Pump–Probe Vibrational Spectroscopy of Hydrogen-Bonded Liquids

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