Topical Review: Molecular reaction and solvation visualized by time-resolved X-ray solution scattering: Structure, dynamics, and their solvent dependence

Kim, Kyung Hwan; Kim, Jeongho; Lee, Jae Hyuk; Ihee, Hyot Cherl

doi:10.1063/1.4865234

Cited by 38 publications

(30 citation statements)

References 133 publications

(53 reference statements)

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“…Areas that are not covered here include time-resolved X-ray probing of 4d and 5d metal systems [2] and of materials for solar energy conversion [2,3], time-resolved X-ray spectroscopy of small molecules and organic systems in solution probing C, N, O and S K-edges [11][12][13], surface chemical reactions [14][15][16], femto-, pico-and nanosecond time-resolved X-ray spectroscopy at synchrotron radiation X-ray sources [2,3,[17][18][19][20][21][22][23][24], and time-resolved X-ray scattering of photochemical reactions in solution [25][26][27][28][29][30][31] and in the gas phase [32,33].…”

Section: Time-resolved X-ray Spectroscopy Of Photochemical Reactions Of 3d Transition-metal Complexesmentioning

confidence: 99%

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers

Wernet

2019

Phil. Trans. R. Soc. A.

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X-ray free-electron lasers with intense, tuneable and short-pulse X-ray radiation are transformative tools for the investigation of transition-metal complexes and metalloproteins. This becomes apparent in particular when combining the experimental observables from X-ray spectroscopy with modern theoretical tools for calculations of electronic structures and X-ray spectra from first principles. The combination gives new insights into how charge and spin densities change in chemical reactions and how they determine reactivity. This is demonstrated for the investigations of structural dynamics with metal K-edge absorption spectroscopy, spin states in excited-state dynamics with metal 3p-3d exchange interactions, the frontier-orbital interactions in dissociation and substitution reactions with metal-specific X-ray spectroscopy, and studies of metal oxidation states with femtosecond pulses for ‘probe-before-destroy’ spectroscopy. The role of X-ray free-electron lasers is addressed with thoughts about how they enable ‘bringing back together’ different aspects of the same problem and this is thought to go beyond a conventional review paper where these aspects are formulated in italic font type in a prequel, an interlude and in a sequel. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays'.

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Section: Time-resolved X-ray Spectroscopy Of Photochemical Reactions Of 3d Transition-metal Complexesmentioning

confidence: 99%

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers

Wernet

2019

Phil. Trans. R. Soc. A.

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“…The experimental procedure for such solution-state investigations has been described in detail previously [32,33]. Briefly, the sample is excited by a short (<2 ps) 390-nm laser pulse (pump) followed by a ∼100-ps 18.2-keV pink-beam (FWHM ∼3%) x-ray pulse (probe) at a well-defined time delay t after the photoexcitation event.…”

Section: Methodsmentioning

confidence: 99%

X-ray tracking of structural changes during a subnanosecond solid-solid phase transition in cobalt nanoparticles

et al. 2019

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“…To investigate the reaction dynamics and structures of reaction intermediates, and subtle effects of atomic substitution, the molecular structures of reacting molecules must be characterized. In this regard, time-resolved X-ray liquidography (TRXL), also known as time-resolved X-ray solution scattering, is an excellent technique because it can be used to both provide global reaction pathways of chemical reactions and reveal the structures of transient intermediates in the liquid solution phase [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 ]. Thus far, TRXL has been used for studying the structural dynamics of a wide variety of systems spanning diatomic molecules, organometallic complexes, proteins, and nanoparticles in the solution phase [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 51 , 52 ...…”

Section: Introductionmentioning

confidence: 99%

Structural Dynamics of C2F4I2 in Cyclohexane Studied via Time-Resolved X-ray Liquidography

Lee

Eom

et al. 2021

IJMS

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The halogen elimination of 1,2-diiodoethane (C2H4I2) and 1,2-diiodotetrafluoroethane (C2F4I2) serves as a model reaction for investigating the influence of fluorination on reaction dynamics and solute–solvent interactions in solution-phase reactions. While the kinetics and reaction pathways of the halogen elimination reaction of C2H4I2 were reported to vary substantially depending on the solvent, the solvent effects on the photodissociation of C2F4I2 remain to be explored, as its reaction dynamics have only been studied in methanol. Here, to investigate the solvent dependence, we conducted a time-resolved X-ray liquidography (TRXL) experiment on C2F4I2 in cyclohexane. The data revealed that (ⅰ) the solvent dependence of the photoreaction of C2F4I2 is not as strong as that observed for C2H4I2, and (ⅱ) the nongeminate recombination leading to the formation of I2 is slower in cyclohexane than in methanol. We also show that the molecular structures of the relevant species determined from the structural analysis of TRXL data provide an excellent benchmark for DFT calculations, especially for investigating the relevance of exchange-correlation functionals used for the structural optimization of haloalkanes. This study demonstrates that TRXL is a powerful technique to study solvent dependence in the solution phase.

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Topical Review: Molecular reaction and solvation visualized by time-resolved X-ray solution scattering: Structure, dynamics, and their solvent dependence

Cited by 38 publications

References 133 publications

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers

Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers

X-ray tracking of structural changes during a subnanosecond solid-solid phase transition in cobalt nanoparticles

Structural Dynamics of C2F4I2 in Cyclohexane Studied via Time-Resolved X-ray Liquidography

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