Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

Biasin, Elisa; Fox, Zachary W.; Andersen, Amity; Ledbetter, Kathryn; Kjær, Kasper Skov; Alonso-Mori, Roberto; Carlstad, Julia M.; Chollet, Matthieu; Gaynor, James D.; Glownia, James M.; Hong, Kiryong; Kröll, Thomas; Lee, Jae Hyuk; Liekhus-Schmaltz, Chelsea; Reinhard, Marco; Sokaras, Dimosthenis; Zhang, Yu; Doumy, Gilles; March, Anne Marie; Southworth, Stephen H.; Mukamel, Shaul; Gaffney, Kelly J.; Schoenlein, R. W.; Govind, Niranjan; Cordones, Amy A.; Khalil, Munira

doi:10.1038/s41557-020-00629-3

Cited by 74 publications

(103 citation statements)

References 59 publications

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“…The simulation results show that the charge distribution affects the solvent arrangement around the solute and accordingly alters the cage term in the TRXL signal, demonstrating the possibility of determining the charge distribution from the TRXL data based on the change of the cage term. In this regard, a recent TRXL study provided evidence that the difference in charge distribution affects the cage orientation, which was tracked by the change of the cage term, and revealed the direction of charge transfer in a FeRu complex with the aid of molecular dynamics (MD) simulations and time-dependent density functional theory calculations 36 . Here, we aimed to determine the quantitative atomic charges of individual atoms comprising a molecule purely based on the TRXL data.…”

Section: Resultsmentioning

confidence: 99%

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

et al. 2022

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Energy, structure, and charge are fundamental quantities characterizing a molecule. Whereas the energy flow and structure change in chemical reactions are experimentally characterized, determining the atomic charges of a molecule in solution has been elusive, even for a triatomic molecule such as triiodide ion, I3−. Moreover, it remains to be answered how the charge distribution is coupled to the molecular geometry; which I-I bond, if two I-I bonds are unequal, dissociates depending on the electronic state. Here, femtosecond anisotropic x-ray solution scattering allows us to provide the following answers in addition to the overall rich structural dynamics. The analysis unravels that the negative charge of I3− is highly localized on the terminal iodine atom forming the longer bond with the central iodine atom, and the shorter I-I bond dissociates in the excited state, whereas the longer one in the ground state. We anticipate that this work may open a new avenue for studying the atomic charge distribution of molecules in solution and taking advantage of orientational information in anisotropic scattering data for solution-phase structural dynamics.

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Section: Resultsmentioning

confidence: 99%

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

et al. 2022

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“…The charge transport mechanism in molecular systems is often a complex combination of inter-and intramolecular electron-transfer processes. [1][2][3][4] Chargetransfer rates for intramolecular transport are expected to be much higher than those provided by intermolecular conduction, as shown in recent experimental and theoretical studies. [5][6][7][8][9][10] Accordingly, it is consensual that intermolecular charge transport must be optimized in targeting high-efficiency semiconductor applications, for example, photovoltaics, [11] lightemitting diodes, [12] transistors, [13] and spintronic systems.…”

Section: Introductionmentioning

confidence: 90%

“…[31] However, as λ also depends on the molecular surroundings, the bulk and the isolated molecule notably consist of two extreme limits regarding environment screening. [4] As remarkable as this, the bridge that connects molecular electronics and (spectro)electrochemistry, which can provide a self-consistent approach to measure λ using a molecular electrochemical nanodevice, is not built so far.…”

Section: Introductionmentioning

confidence: 99%

Reorganization Energy upon Controlled Intermolecular Charge‐Transfer Reactions in Monolithically Integrated Nanodevices

Merces

Candiotto

Ferro

et al. 2021

Small

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Intermolecular electron‐transfer reactions are key processes in physics, chemistry, and biology. The electron‐transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron‐transfer reactions on charge‐carrier hopping, well‐controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self‐rolling nanomembrane devices with strain‐engineered mechanical properties, on‐a‐chip monolithic integration, and multi‐environment operation features can overcome this challenge. The ongoing advances in nanomembrane‐origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular‐level charge transport characterization. Thereby, employing nCap, the copper‐phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature‐dependent measurements of CuPc nanometer‐thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge‐transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.

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“…In this spirit, organic chemists are well aware that reaction rates change according to the solvent [33][34][35] . New computational and experimental methods continue to be introduced 36 . On physical grounds, we consider it likely that chemical reactions produce electrified polarization of solvent molecules that solvate the molecules that react, thus providing a mechanism that funnels the rapid (fs) energy release of electronic rearrangement to slower, persistent reorganization of these larger and more diffuse solvation structures.…”

mentioning

confidence: 99%

Linking Chemical Reaction Intermediates of the Click Reaction to Their Molecular Diffusivity

Huang¹,

Li²,

Wang³

et al. 2021

Preprint

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Bipolar reactions have been provoked by reports of boosted diffusion during chemical and enzymatic reactions. To some, it is intuitively reasonable that relaxation to truly Brownian motion after passing an activation barrier can be slow, but to others the notion is so intuitively unphysical that they suspect the supporting experiments to be artifact. Here we study a chemical reaction according to whose mechanism some intermediate species should speed up while others slow down in predictable ways, if the boosted diffusion interpretation holds. Experimental artifacts would do not know organic chemistry mechanism, however. Accordingly, we scrutinize the absolute diffusion coefficient (D) during intermediate stages of the CuAAC reaction (coppercatalyzed azide-alkyne cycloaddition click reaction), using proton pulsed field-gradient nuclear magnetic resonance (PFG-NMR) to discriminate between the diffusion of various reaction intermediates. For the azide reactant, its D increases during reaction, peaks at the same time as peak reaction rate, then returns to its initial value. For the alkyne reagent, its D decreases consistent with presence of the intermediate large complexes formed from copper catalyst and its ligand, except for the 2Cu-alk complex whose more rapid D may signify that this species is the real reactive complex. For the product of this reaction, its D increases slowly as it detaches from the triazolide catalyst complex. These examples of enhanced diffusion for some molecular species and depressed diffusion for others causes us to conclude that diffusion coefficients during these elementary reactions are influenced by two components: hydrodynamic radius increase from complex formation, which slows diffusion, and energy release rate during the chemical reaction, which speeds it up. We discuss possible mechanisms and highlight that too little is yet understood about slow solvent reorganization during chemical reactions.<br>

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Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

Cited by 74 publications

References 59 publications

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

Reorganization Energy upon Controlled Intermolecular Charge‐Transfer Reactions in Monolithically Integrated Nanodevices

Linking Chemical Reaction Intermediates of the Click Reaction to Their Molecular Diffusivity

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