Unravelling the mechanisms of vibrational relaxation in solution

We present a systematic study of the mode-specific vibrational relaxation of NO(2) in six weakly-interacting solvents (perfluorohexane, perfluoromethylcyclohexane, perfluorodecalin, carbon tetrachloride, chloroform, and d-chloroform), chosen to elucidate the dominant energy transfer mechanisms in the solution phase. Broadband transient vibrational absorption spectroscopy has allowed us to extract quantum state-resolved relaxation dynamics of the two distinct NO(2) fragments produced from the 340 nm photolysis of N(2)O(4) → NO(2)(X) + NO(2)(A) and their separate paths to thermal equilibrium. Distinct relaxation pathways are observed for the NO(2) bending and stretching modes, even at energies as high as 7000 cm(–1) above the potential minimum. Vibrational energy transfer is governed by different interaction mechanisms in the various solvent environments, and proceeds with timescales ranging from 20–1100 ps. NO(2) relaxation rates in the perfluorocarbon solvents are identical despite differences in acceptor mode state densities, infrared absorption cross sections, and local solvent structure. Vibrational energy is shown to be transferred to non-vibrational solvent degrees of freedom (V-T) through impulsive collisions with the perfluorocarbon molecules. Conversely, NO(2) relaxation in chlorinated solvents is reliant on vibrational resonances (V-V) while V-T energy transfer is inefficient and thermal excitation of the surrounding solvent molecules inhibits faster vibrational relaxation through direct complexation. Intramolecular vibrational redistribution allows the symmetric stretch of NO(2) to act as a gateway for antisymmetric stretch energy to exit the molecule. This study establishes an unprecedented level of detail for the cooling dynamics of a solvated small molecule, and provides a benchmark system for future theoretical studies of vibrational relaxation processes in solution

Attosecond spectroscopy reveals alignment dependent core-hole dynamics in the ICl molecule

The removal of electrons located in the core shells of molecules creates transient states that live between a few femtoseconds to attoseconds. Owing to these short lifetimes, time-resolved studies of these states are challenging and complex molecular dynamics driven solely by electronic correlation are difficult to observe. Here, we obtain few-femtosecond core-excited state lifetimes of iodine monochloride by using attosecond transient absorption on iodine 4 d −1 6 p transitions around 55 eV. Core-level ligand field splitting allows direct access of excited states aligned along and perpendicular to the ICl molecular axis. Lifetimes of 3.5 ± 0.4 fs and 4.3 ± 0.4 fs are obtained for core-hole states parallel to the bond and 6.5 ± 0.6 fs and 6.9 ± 0.6 fs for perpendicular states, while nuclear motion is essentially frozen on this timescale. Theory shows that the dramatic decrease of lifetime for core-vacancies parallel to the covalent bond is a manifestation of non-local interactions with the neighboring Cl atom of ICl

Distinguishing Population and Coherence Transfer Pathways in a Metal Dicarbonyl Complex Using Pulse-Shaped Two-Dimensional Infrared Spectroscopy

Collection of two-dimensional infrared (2DIR) spectra using two ultrafast, broadband infrared pump pulses followed by an ultrafast probe pulse optimizes the experimental time and frequency resolution, but can also introduce quantum beat and coherence transfer pathways. The associated coherent dynamics create intensity oscillations and add extra features to 2DIR spectra. We describe a method to suppress these pathways using pump–pulse shaping, without significantly degrading the time and spectral resolution. We illustrate the method for a rhodium dicarbonyl complex, acetylacetonato dicarbonyl rhodium (RDC), to establish the relative importance of coherence and population transfer between carbonyl symmetric and asymmetric stretching modes. Our technique effectively suppresses the quantum beats. Comparison of peak intensities obtained with shaped and unshaped pump pulses demonstrates that coherence transfer does not play a significant role in the 2DIR spectrum of RDC in this spectral region