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

Dettori, Riccardo; Ceriotti, Michele; Hunger, Johannes; Melis, Claudio; Colombo, Luciano; Donadio, Davide

doi:10.1021/acs.jctc.6b01108

Cited by 22 publications

(41 citation statements)

References 54 publications

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“…Further insight into the character of the crystal dynamics in more realistic systems is obtained from the results of MDS in and out of equilibrium within a 3 ×3×2 pentacene crystal cell of the same polymorph. Out-of-equilibrium MDS were obtained from microcanonical dynamics following a thermalization by a hotspot thermostat ( 39 ) centered at 1 THz. A connection to the FED experiments can be obtained by simulating diffraction patterns for each MDS snapshot ( 37 , 40 ), as illustrated in Fig.…”

Section: Resultsmentioning

confidence: 99%

Nuclear dynamics of singlet exciton fission in pentacene single crystals

et al. 2021

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Singlet exciton fission (SEF) is a key process for developing efficient optoelectronic devices. An aspect rarely probed directly, yet with tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here, we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynamics simulations, time-dependent density-functional theory, and experimental structure factor analysis, the coherent motions are identified as collective sliding motions of the pentacene molecules along their long axis. Such motions modify the excitonic coupling between adjacent molecules. Our findings reveal that long-range motions play a decisive part in the electronic decoupling of the electronically correlated triplet pairs and shed light on why SEF occurs on ultrafast time scales.

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Section: Resultsmentioning

confidence: 99%

Nuclear dynamics of singlet exciton fission in pentacene single crystals

et al. 2021

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“…Similarly in solution, while solvent induced effects could be estimated using force field MD simulations, 56 typically direct energy transfer can occur on the same timescale of about 10 ps, [57][58][59][60] so it is difficult to disentangle from solvent-mediated IVR, which can occur on the timescale of about 1 ps. 54,[61][62][63][64][65] The reported results provide fundamental understanding of energy transfer that may limit the effectiveness of catalysts mounted on metals.…”

Section: System A'(1) A''/a'(2)mentioning

confidence: 99%

Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces

Rudshteyn

Zhu

et al. 2018

J. Phys. Chem. Lett.

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A combination of time-resolved vibrational spectroscopy and density functional theory techniques have been applied to study the vibrational energy relaxation dynamics of the Re(4,4'-dicyano-2,2'-bipyridine)(CO)Cl (Re(CO)Cl) catalyst for CO to CO conversion bound to gold surfaces. The kinetics of vibrational relaxation exhibits a biexponential decay including an ultrafast initial relaxation and complete recovery of the ground vibrational state. Ab initio molecular dynamics simulations and time-dependent perturbation theory reveal the former to be due to vibrational population exchange between CO stretching modes and the latter to be a combination of intramolecular vibrational relaxation (IVR) and electron-hole pair (EHP)-induced energy transfer into the gold substrate. EHP-induced energy transfer from the Re(CO)Cl adsorbate into the gold surface occurs on the same time scale as IVR of Re(CO)Cl in aprotic solvents. Therefore, it is expected to be particularly relevant to understanding the reduced catalytic activity of the homogeneous catalyst when anchored to a metal surface.

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“…The net result is a few vibrations at higher temperature than the rest of the system, which is precisely what is needed to study VET from MD. Dettori et al 70,71 have demonstrated these methods for a pumpprobe style simulation of hydrogen-bonded liquids and here we follow a similar protocol to selectively target vibrations of interest. Each of these GLE pumped vibrations emulate a Gaussian centered pump of width 33 cm -1 , which act on a 3 × 3 × 3 super-cell of RDX for 10 ps to establish a non-equipartition of vibrational kinetic energy; the pump is subsequently removed and spectra are collected in the micro-canonical ensemble.…”

Section: B Computationalmentioning

confidence: 99%

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

Cole-Filipiak¹,

Knepper²,

Wood³

et al. 2021

Preprint

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Herein, we report on the sub-picosecond to sub-nanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct timescales: sub-picosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the hundred picosecond timescale. Mode-selectivity of the longest dynamics suggests coupling of the N–N and axial NO<sub>2</sub> stretching modes with the long-lived, excited phonon bath.

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

Cited by 22 publications

References 54 publications

Nuclear dynamics of singlet exciton fission in pentacene single crystals

Nuclear dynamics of singlet exciton fission in pentacene single crystals

Electron–Hole-Pair-Induced Vibrational Energy Relaxation of Rhenium Catalysts on Gold Surfaces

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

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