Energy Relaxation and Thermal Diffusion in Infrared Pump-Probe Spectroscopy of Hydrogen-Bonded Liquids.

  title={Energy Relaxation and Thermal Diffusion in Infrared Pump-Probe Spectroscopy of Hydrogen-Bonded Liquids.},
  author={Riccardo Dettori and M. Ceriotti and Johannes Hunger and Luciano Colombo and D. Donadio},
  journal={The journal of physical chemistry letters},
Infrared pump-probe spectroscopy provides detailed information about the dynamics of hydrogen-bonded liquids. Due to dissipation of the absorbed pump pulse energy, thermal equilibration dynamics also contributes to the observed signal. Disentangling this contribution from the molecular response remains a challenge. By performing non-equilibrium molecular dynamics simulations of liquid-deuterated methanol, we show that faster molecular vibrational relaxation and slower heat diffusion are… 

Figures from this paper

Direct observation of ultrafast hydrogen bond strengthening in liquid water.

The experiment and simulations unveil the intermolecular character of the water vibration preceding the relaxation of the OH stretch, revealing the need to treat the distribution of the shared proton in the hydrogen bond quantum mechanically to capture the structural dynamics on femtosecond timescales.

Hydrogen bonds and dynamics of liquid water and alcohols

Ultrafast dynamics of electrons and phonons: from the two-temperature model to the time-dependent Boltzmann equation

ABSTRACT The advent of pump-probe spectroscopy techniques paved the way to the exploration of ultrafast dynamics of electrons and phonons in crystalline solids. Following photo-absorption of a pump

Sub-picosecond to Sub-nanosecond Vibrational Energy Transfer Dynamics in Pentaerythritol Tetranitrate.

Using ultrafast infrared pump-probe spectroscopy on pentaerythritol tetranitrate (PETN), sub-picosecond vibrational energy transfer (VET) is revealed from the photoexcited band at 1660cm-1 into every other infrared-active mode in the probed frequency range 800-1800 cm-1.

Fourier-like Thermal Relaxation of Nanoscale Explosive Hot Spots

We develop here an approach to directly determine the thermal transport properties of explosive hot spots with realistic initial structures through a combination of molecular dynamics (MD) and

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules

This framework discusses recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles, focusing on femtosecond Transient Absorption Spectroscopy enabling us to follow the transition from a Locally Excited state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms.

Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) Thin Films.

The coupling of inter- and intramolecular vibrations plays a critical role in initiating chemistry during the shock-to-detonation transition in energetic materials. Herein, we report on the

N-Doped Yellow-Emissive Carbon Nanodots from Gallic Acid: Reaction Engineering, Stimuli-Responsive Red Emission, and Intracellular Localization

An easy one-pot method is utilized for the synthesis of carbon nanodots, which has been investigated primarily from material perspectives. However, this preferred one-pot synthesis method suffers f...



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

A nonequilibrium molecular dynamics simulation approach, based on the generalized Langevin equation, is introduced, to study vibrational energy relaxation in pump-probe spectroscopy, providing a robust picture of energy relaxation at the molecular scale.

Ultrafast Energy Equilibration in Hydrogen-Bonded Liquids

We have studied the equilibration dynamics of liquid water and alcohols following a local deposition of energy using time-resolved femtosecond mid-infrared pump−probe spectroscopy. The equilibration

Ultrafast structural dynamics of water induced by dissipation of vibrational energy.

A two-stage structural response of this network to energy disposal is demonstrated: vibrational energy from individually excited water molecules is transferred to intermolecular modes, resulting in a sub-100 fs nuclear rearrangement that leaves the local hydrogen bonds weakened but unbroken.

A Microscopic Interpretation of Pump-Probe Vibrational Spectroscopy Using Ab Initio Molecular Dynamics.

It is found that the energy relaxation is highly heterogeneous and strongly depends on the local environment, where a strong hydrogen bond network can transport energy with a time scale of 200 fs, whereas a weaker network can slow down the transport by a factor 2-3.

Interpreting Quasi-Thermal Effects in Ultrafast Spectroscopy of Hydrogen-Bonded Systems.

The thermal and quasi-thermal responses of the hydrogen-bonded homodimer of 7-azaindole with temperature-dependent FTIR spectroscopy and ultrafast mid-IR continuum spectroscopic are examined to provide insight into the changes in the vibrational spectrum from different origins.

Local hydrogen bonding dynamics and collective reorganization in water: ultrafast infrared spectroscopy of HOD/D(2)O.

An investigation into hydrogen bonding dynamics and kinetics in water using femtosecond infrared spectroscopy of the OH stretching vibration of HOD in D(2)O finds a kinetic regime which gives an effective rate for exchange of intermolecular structures.

Vibrational Relaxation and Hydrogen-Bond Dynamics of HDO:H2O

Femtosecond two-color mid-infrared pump−probe spectroscopy is used to study the vibrational relaxation and the hydrogen-bond dynamics of HDO dissolved in liquid H2O. By looking at the spectral

A novel method for analyzing energy relaxation in condensed phases using nonequilibrium molecular dynamics simulations: application to the energy relaxation of intermolecular motions in liquid water.

We present a novel method to investigate energy relaxation processes in condensed phases using nonequilibrium molecular dynamics simulations. This method can reveal details of the time evolution of