A Study To Control Chemical Reactions Using Si:2p Core Ionization: Site-Specific Fragmentation

Nagaoka, Shin‐ichi; Fukuzawa, H.; Prümper, G.; Takemoto, Masaya; Takahashi, Osamu; Yamaguchi, Katsuhiro; Kakiuchi, Takuhiro; Tabayashi, Kiyohiko; Suzuki, Isao; Harries, James; Tamenori, Y.; Ueda, Kiyoshi

doi:10.1021/jp203664r

Cited by 31 publications

(48 citation statements)

References 36 publications

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“…17 carried out a study on ozone, and Nagaoka et al [18][19][20] investigated the dissociation of some trihalosilyltrimethylsilyl-compounds upon core ionisation of the silicon 1s and 2p inner shells. Site-specific photochemistry arising from initial ionisation at the allimportant carbon atoms of organic molecules was studied by Itälä et al 21 for the case of pyrimidine and by some of us 22 for the case of ethyl trifluoroacetate.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)

Zagorodskikh

Eland

Zhaunerchyk

et al. 2016

The Journal of Chemical Physics

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Citation for the original published paper (version of record):Zagorodskikh, S., Eland, J H., Zhaunerchyk, V., Mucke, M., Squibb, R J. et al. (2016) Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal). Journal of Chemical PhysicsAccess to the published version may require subscription. N.B. When citing this work, cite the original published paper. Permanent link to this version:http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-301121Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal) Site-specific fragmentation upon 1s photoionisation of acetaldehyde has been studied using synchrotron radiation and a multi-electron-ion coincidence technique based on a magnetic bottle. Experimental evidence is presented that bond rupture occurs with highest probability in the vicinity of the initial charge localisation and possible mechanisms are discussed. We find that a significant contribution to site-specific photochemistry is made by different fragmentation patterns of individual quantum states populated at identical ionisation energies.

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Section: Introductionmentioning

confidence: 99%

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)

Zagorodskikh

Eland

Zhaunerchyk

et al. 2016

The Journal of Chemical Physics

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“…More generally, x-ray photoionization proceeds via electron promotion into the continuum and relaxation by Auger decay. Experimentally this process has been studied [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] with electron-ion coincidence methods. Site-selectivity is obtained by exciting or ionizing atoms of different elements [10][11][12]22 or, for atoms of same elements, by using site-specific chemical shifts in a variety of medium-sized carbon 9,17,18,20,24,25 and silicon-containing 13,16,19 molecules.…”

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confidence: 99%

Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation

Inhester

Oostenrijk

Patanen

et al. 2018

J. Phys. Chem. Lett.

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In many cases fragmentation of molecules upon inner-shell ionization is very unspecific with respect to the initially localized ionization site. Often this finding is interpreted in terms of an equilibration of internal energy into vibrational degrees of freedom after Auger decay. We investigate the X-ray photofragmentation of ethyl trifluoroacetate upon core electron ionization at environmentally distinct carbon sites using photoelectron-photoion-photoion coincidence measurements and ab initio electronic structure calculations. For all four carbon ionization sites, the Auger decay weakens the same bonds and transfers the two charges to opposite ends of the molecule, which leads to a rapid dissociation into three fragments, followed by further fragmentation steps. The lack of site specificity is attributed to the character of the dicationic electronic states after Auger decay instead of a fast equilibration of internal energy.

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“…The site-specific excitation has been proposed as a tool for selectively breaking particular bonds of a molecule. A number of studies have been performed on this topic using both resonant core excitation [5][6][7][8][9][10][11][12][13][14][15][16][17] and core ionization [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31], showing varying degree of selectivity. A recent study [31] on core ionization of molecules has shown only a small degree of selectivity which was explained by the delocalized character of the valence orbitals.…”

Section: Introductionmentioning

confidence: 99%

Resonant Auger electron-ion-coincidence spectroscopy of N -methyltrifluoroacetamide: Site-specific fragmentation studies

et al. 2020

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We present a theoretical and experimental study of the electronic structure of N-methyltrifluoroacetamide (FNMA) and examine the resonant Auger (RA) decay upon site-and state-specific excitation at the C 1s, N 1s, and O 1s edges. Based on the calculated energies for cationic states of 1h and 2h-1p configurations, we assign the peaks of recorded VUV photoelectron and RA spectra. Specifically, we identify the spectral features associated with participator and spectator RA decay. To aid in a deeper understanding of previous observations of limited site-specific bond breaking in FNMA, the influence of the site-specific excitation and the character of the Auger decay on the fragmentation is investigated using Auger electron ion coincidence experiments. Moreover, to investigate the potentially different capacity for selective bond cleavage of participator and spectator Auger states, we apply this technique to the spectator Auger state with the main electronic configuration of (31a) −1 (32a) −1 (34a) 1 , which is well resolved in the experimental spectrum. Finally, the influence of the molecular excess energy and the electronic character of the RA final states on fragmentation is addressed. Based on our findings, we argue that the excess energy the FNMA molecule gains upon RA decay is the dominant factor determining the fragmentation pattern.

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A Study To Control Chemical Reactions Using Si:2p Core Ionization: Site-Specific Fragmentation

Cited by 31 publications

References 36 publications

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal)

Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation

Resonant Auger electron-ion-coincidence spectroscopy of N -methyltrifluoroacetamide: Site-specific fragmentation studies

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