Vibrational predissociation versus intramolecular vibrational energy redistribution (IVR) in rare gas∙∙∙dihalogen complexes: IVR identified in Ar∙∙∙I2(B,ν′) using velocity-map imaging

The competition between multiple pathways sampled during the energetic relaxation of excited molecules can be difficult to experimentally decipher. The rare gas···dihalogen van der Waals complexes have remained key systems...

Intramolecular vibrational energy redistribution and the quantum ergodicity transition: a phase space perspective

The onset of facile intramolecular vibrational energy flow can be related to features in the connected network of anharmonic resonances in the classical phase space.

Viscosity Dependence of the Ultrafast Vibrational Dynamics of Borohydride in NaOH Solutions: Crowding Effect on Dihydrogen Bonds

<p>Two-dimensional infrared spectroscopy (2D-IR) probes the local solvent structure and dynamics of the nu₃ mode (BH antisymmetric stretch) of borohydride (BH₄^- ) in aqueous solution. The 2D-IR spectra of the BH stretches have broad and overlapping bands. Vibrational energy relaxation occurs on a 2 ps timescale. Energy that is initially deposited in BH stretching modes and directly in the solvent generates a long lived hot ground state. Before the hot ground state appears, some indications of intramolecular vibrational energy redistribution are observed. The solvent viscosity was varied (1.5–6 cP) by increasing the hydroxide concentration (0.1–7 M). Within the vibrational lifetime of the BH stretching modes, the rate of structural relaxation slows proportionally to the viscosity due to the overlap of the ions’s solvation shells.</p>

Viscosity Dependence of the Ultrafast Vibrational Dynamics of Borohydride in NaOH Solutions: Crowding Effect on Dihydrogen Bonds

<p>Two-dimensional infrared spectroscopy (2D-IR) probes the local solvent structure and dynamics of the nu₃ mode (BH antisymmetric stretch) of borohydride (BH₄^- ) in aqueous solution. The 2D-IR spectra of the BH stretches have broad and overlapping bands. Vibrational energy relaxation occurs on a 2 ps timescale. Energy that is initially deposited in BH stretching modes and directly in the solvent generates a long lived hot ground state. Before the hot ground state appears, some indications of intramolecular vibrational energy redistribution are observed. The solvent viscosity was varied (1.5–6 cP) by increasing the hydroxide concentration (0.1–7 M). Within the vibrational lifetime of the BH stretching modes, the rate of structural relaxation slows proportionally to the viscosity due to the overlap of the ions’s solvation shells.</p>

Direct observation of structural dynamics upon photo-excitation in a spin crossover crystal with femtosecond electron diffraction

Photoinduced spin transitions are studied by femtosecond electron diffraction to understand ultrafast structural dynamics associated with intersystem crossing. The results indicate the structural reorganization occurs within 2.3 ps, as the metal-ligand bond distribution narrows during intramolecular vibrational energy redistribution.

Understanding the intramolecular vibrational energy transfer and structural dynamics of anionic ligands in a photo-catalytic CO2 reduction catalyst

The knowledge of intramolecular vibrational energy redistribution (IVR) and structural dynamics of rhenium photo-catalysts is essential for understanding the mechanism of the photo-catalytic process of CO2 reduction.

Role of electron in intramolecular vibrational energy redistribution: a simulation of time- and frequency-resolved CARS spectrum

The electron plays a mediator role in the IVR process and significantly increases the vibrational energy transfer efficiency.

Intramolecular vibrational energy redistribution in HCCCH2X (X = Cl, Br, I) measured by femtosecond pump–probe experiments in a hollow waveguide

Time resolved femtosecond probing of intramolecular energy flow after excitation of the two different infrared CH-chromophores in these bichromophoric molecules shows strong dependence on the chemical environment of the initial excitation.