Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy

Bhattacherjee, Aditi; Schnorr, Kirsten; Oesterling, Sven; Yang, Zheyue; Xue, Ting; Vivie‐Riedle, Regina de; Leone, Stephen R.

doi:10.1021/jacs.8b07155

Cited by 50 publications

(59 citation statements)

References 48 publications

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“…There has been significant growth recently in application of table-top XUV/X-ray transient absorption spectroscopy [1][2][3][4][5] to probe valence and Rydberg core-excited states due to advances in high harmonic generation (HHG). A range of ultrafast photo-induced chemistry, such as bond breaking, 3,5 ring opening, 2,6 internal conversion (IC), and intersystem crossing (ISC), 4 has been studied with the aforementioned method. The bond breaking dynamics of CH 3 I has been studied for a few decades with different experimental methods, such as photofragment spectroscopy, 7 magnetic circular dichroism spectroscopy, 8 mass spectrometer, 9 velocity map imaging spectroscopy, [10][11][12][13] and so forth.…”

Section: Introductionmentioning

confidence: 99%

A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation

Wang

Odelius

2019

The Journal of Chemical Physics

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UV pump-XUV/X-ray probe measurements have been successfully applied in the study of photo-induced chemical reactions. Although rich element-specific e lectronic s tructure i nformation i s a ccessible w ithin X UV/X-ray (inner-shell) a bsorption s pectra, i t c an b e difficult to interpret the chemistry directly from the spectrum without supporting theoretical simulations. A multireference method to completely simulate UV pump-XUV/X-ray probe measurement has been developed and applied to study the methyl iodide photodissociation process. Multireference, fewest-switches surface hopping (FSSH) trajectories were used to explore the coupled electronic and ionic dynamics upon photoexcitation of methyl iodide. Interpretation of previous measurements is provided by associated multireference, restricted active space, inner-shell spectral simulations. This combination of multireference FSSH trajectories and XUV spectra provides an interpretation of transient features appearing in previous measurements within the first 100 fs after photoexcitation and validates the significant branching ratio in the final excited-state population. This methodology should prove useful for interpretation of the increasing number of inner-shell probe studies of molecular excited states or for directing new experiments toward interesting regions of the potential energy landscape.

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Section: Introductionmentioning

confidence: 99%

A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation

Wang

Odelius

2019

The Journal of Chemical Physics

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“…The core binding energies in Table 5 in the recent near-edge X-ray absorption finestructure (NEXAFS) spectrum of furfural. [62] The corresponnding C1s and O1s energies of the trans-and cis-FUR . The method used is the same with the recent NMR study of resveratrol.…”

Section: Methoxyphenol Conformers In the Core And Valence Spacementioning

confidence: 99%

Probing Intramolecular Interaction of Stereoisomers Using Computational Spectroscopy

2020

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Several model stereoisomers such as ferrocene (Fc), methoxyphenol, and furfural conformers are discussed. It was discovered that the Fc IR spectroscopic band(s) below 500cm−1 serve as fingerprints for eclipsed (splitting 17 (471–488)cm−1) and staggered Fc (splitting is ~2 (459–461)cm−1) in the gas phase. It is revealed that in the gas phase the dominance of the eclipsed Fc (D5h) at very low temperatures changes to a mixture of both eclipsed and staggered Fc when the temperature increases. However, in solvents such as CCl4, eclipsed Fc dominates at room temperature (300K) due to the additional solvation energy. Intramolecular interactions of organic model compounds such as methoxyphenols (guaiacol (GUA) and mequinol (MEQ)) and furfural, ionization energies such as the carbon 1s (core C1s), as well as valence binding energy spectra serve this purpose well. Hydrogen bonding alters the C1s binding energies of the methoxy carbon (C(7)) of anti-syn and anti-gauche conformers of GUA to 292.65 and 291.91eV, respectively. The trans and cis MEQ conformers, on the other hand, are nearly energy degenerate, whereas their dipole moments are significantly different: 2.66 Debye for cis and 0.63 Debye for trans-MEQ. Moreover, it is found that rotation around the Cring–OH and the Cring–OCH3 bonds differ in energy barrier height by ~0.50 kcal⋅mol−1. The Dyson orbital momentum profiles of the most different ionic states, 25a′ (0.35eV) and 3a′ (−0.33eV), between cis and trans-MEQ in outer valence space (which is measurable using electron momentum spectroscopy (EMS)), exhibit quantitative differences. Finally, the molecular switch from trans and cis-furfural engages with a small energy difference of 0.74 kcal mol−1, however, at the calculated C(3)(–H⋅⋅⋅O=C) site the C1s binding energy difference is 0.105eV (2.42 kcal mol−1) and the NMR chemical shift of the same carbon site is also significant; 7.58ppm from cis-furfural without hydrogen bonding.

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“…[10][11][12][13][14][15][16][17] Nowadays, this type of experimental setup is commonly used to track chemical dynamics on femtosecond and attosecond timescales. 5,[17][18][19][20] For example, it has been applied to study fundamental molecular processes, such as ultrafast internal conversion and intersystem crossing in nucleobases 17 and other organic molecules, 19 metal-to-ligand and metal-to-metal charge transfer, ring open-ing, 21,22 hydrogen-bonding networks in solvated species, 23 and ultrafast proton transfer. 20 Core-valence transitions can also be exploited to probe transient species in minute amounts, and in the presence of parent closed-shell species, as recently demonstrated by detecting OH produced in the radiolysis of water.…”

Section: Introductionmentioning

confidence: 99%

“…6,7,19,21,22,[35][36][37] For example, the wide spectral range of the HHG flux enabled studying light-induced chemical transformations in CF + 4 and SF + 6 molecules at the carbon K-edge and sulfur L-edge; this study characterized the reaction paths and the effects of symmetry breaking through the splitting of absorption bands and Rydberg-valence mixing induced by the geometry changes. 35 Other chemically relevant examples include characterization of the pericyclic minimum leading to the ultrafast ring-opening (or the ground-state reformation) in 1,3-cyclohexadiene 21 and in furfural, 22 as well as inter-system crossing in acetylacetone. 19 These studies exploited the sensitivity of the transitions involving 1s C electrons to the structural changes in the course of dynamics.…”

Section: Introductionmentioning

confidence: 99%

The Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

Vidal¹,

Epshtein²,

Scutelnic³

et al. 2020

Preprint

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We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys. Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation. The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller effect in benzene cation.

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Photoinduced Heterocyclic Ring Opening of Furfural: Distinct Open-Chain Product Identification by Ultrafast X-ray Transient Absorption Spectroscopy

Cited by 50 publications

References 48 publications

A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation

A combined multi-reference pump-probe simulation method with application to XUV signatures of ultrafast methyl iodide photodissociation

Probing Intramolecular Interaction of Stereoisomers Using Computational Spectroscopy

The Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy

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