Dissociative electron attachment and electronic excitation in Fe(CO)(5)
Authorized Users Only
2018
Authors
Allan, Michael
Lacko, M.

Papp, P.
Matejcik, S.

Zlatar, Matija

Fabrikant, I. I.

Kocisek, J.

Fedor, Juraj

Article (Published version)

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In a combined experimental and theoretical study we characterize dissociative electron attachment (DEA) to, and electronically excited states of, Fe(CO)(5). Both are relevant for electron-induced degradation of Fe(CO)(5). The strongest DEA channel is cleavage of one metal-ligand bond that leads to production of Fe(CO)(4)(-). High-resolution spectra of Fe(CO)(4)(-) reveal fine structures at the onset of vibrational excitation channels. Effective range R-matrix theory successfully reproduces these structures as well as the dramatic rise of the cross section at very low energies and reveals that virtual state scattering dominates low-energy DEA in Fe(CO)(5) and that intramolecular vibrational redistribution (IVR) Ways an essential role. The virtual state hypothesis receives further experimental support from the rapid rise of the elastic cross section at very low energies and intense threshold peaks in vibrational excitation cross sections. The IVR hypothesis is confirmed by our measuremen...ts of kinetic energy distributions of the fragment ions, which are narrow (similar to 0.06 eV) and peak at low energies (similar to 0.025 eV), indicating substantial vibrational excitation in the Fe(CO)4(-) fragment. Rapid IVR is also revealed by the yield of thermal electrons, observed in two-dimensional (2D) electron energy loss spectroscopy. We further measured mass-resolved DEA spectra at higher energies, up to 12 eV, and compared the bands observed there to resonances revealed by the spectra of vibrational excitation cross sections. Dipole-allowed and dipole/spin forbidden electronic transitions in Fe(CO)(5)-relevant for neutral dissociation by electron impact-are probed using electron energy loss spectroscopy and time-dependent density functional theory calculations. Very good agreement between theory and experiment is obtained, permitting assignment of the observed bands.
Source:
Physical Chemistry Chemical Physics, 2018, 20, 17, 11692-11701Publisher:
- Royal Soc Chemistry, Cambridge
Funding / projects:
- Czech Science Foundation - 17-04844S
- Swiss National Science Foundation - 200020-144367/1
- US National Science Foundation - PHY-1401788
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
- COST Action - CM1301 CELINA
- Slovak Grant Agency - VEGA 1/0733/17
- Slovak Research and Development Agency - APVV-15-0580
- EU's Horizon 2020 program 692335
Note:
- The peer-reviewed version of the article: http://cer.ihtm.bg.ac.rs/handle/123456789/2659
- Supplementary information: https://cer.ihtm.bg.ac.rs/handle/123456789/4532
Related info:
- Version of
https://cer.ihtm.bg.ac.rs/handle/123456789/2659 - Referenced by
https://cer.ihtm.bg.ac.rs/handle/123456789/4532
DOI: 10.1039/c8cp01387j
ISSN: 1463-9076
PubMed: 29682656
WoS: 000431824000022
Scopus: 2-s2.0-85046645831
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IHTMTY - JOUR AU - Allan, Michael AU - Lacko, M. AU - Papp, P. AU - Matejcik, S. AU - Zlatar, Matija AU - Fabrikant, I. I. AU - Kocisek, J. AU - Fedor, Juraj PY - 2018 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/2312 AB - In a combined experimental and theoretical study we characterize dissociative electron attachment (DEA) to, and electronically excited states of, Fe(CO)(5). Both are relevant for electron-induced degradation of Fe(CO)(5). The strongest DEA channel is cleavage of one metal-ligand bond that leads to production of Fe(CO)(4)(-). High-resolution spectra of Fe(CO)(4)(-) reveal fine structures at the onset of vibrational excitation channels. Effective range R-matrix theory successfully reproduces these structures as well as the dramatic rise of the cross section at very low energies and reveals that virtual state scattering dominates low-energy DEA in Fe(CO)(5) and that intramolecular vibrational redistribution (IVR) Ways an essential role. The virtual state hypothesis receives further experimental support from the rapid rise of the elastic cross section at very low energies and intense threshold peaks in vibrational excitation cross sections. The IVR hypothesis is confirmed by our measurements of kinetic energy distributions of the fragment ions, which are narrow (similar to 0.06 eV) and peak at low energies (similar to 0.025 eV), indicating substantial vibrational excitation in the Fe(CO)4(-) fragment. Rapid IVR is also revealed by the yield of thermal electrons, observed in two-dimensional (2D) electron energy loss spectroscopy. We further measured mass-resolved DEA spectra at higher energies, up to 12 eV, and compared the bands observed there to resonances revealed by the spectra of vibrational excitation cross sections. Dipole-allowed and dipole/spin forbidden electronic transitions in Fe(CO)(5)-relevant for neutral dissociation by electron impact-are probed using electron energy loss spectroscopy and time-dependent density functional theory calculations. Very good agreement between theory and experiment is obtained, permitting assignment of the observed bands. PB - Royal Soc Chemistry, Cambridge T2 - Physical Chemistry Chemical Physics T1 - Dissociative electron attachment and electronic excitation in Fe(CO)(5) VL - 20 IS - 17 SP - 11692 EP - 11701 DO - 10.1039/c8cp01387j ER -
@article{ author = "Allan, Michael and Lacko, M. and Papp, P. and Matejcik, S. and Zlatar, Matija and Fabrikant, I. I. and Kocisek, J. and Fedor, Juraj", year = "2018", abstract = "In a combined experimental and theoretical study we characterize dissociative electron attachment (DEA) to, and electronically excited states of, Fe(CO)(5). Both are relevant for electron-induced degradation of Fe(CO)(5). The strongest DEA channel is cleavage of one metal-ligand bond that leads to production of Fe(CO)(4)(-). High-resolution spectra of Fe(CO)(4)(-) reveal fine structures at the onset of vibrational excitation channels. Effective range R-matrix theory successfully reproduces these structures as well as the dramatic rise of the cross section at very low energies and reveals that virtual state scattering dominates low-energy DEA in Fe(CO)(5) and that intramolecular vibrational redistribution (IVR) Ways an essential role. The virtual state hypothesis receives further experimental support from the rapid rise of the elastic cross section at very low energies and intense threshold peaks in vibrational excitation cross sections. The IVR hypothesis is confirmed by our measurements of kinetic energy distributions of the fragment ions, which are narrow (similar to 0.06 eV) and peak at low energies (similar to 0.025 eV), indicating substantial vibrational excitation in the Fe(CO)4(-) fragment. Rapid IVR is also revealed by the yield of thermal electrons, observed in two-dimensional (2D) electron energy loss spectroscopy. We further measured mass-resolved DEA spectra at higher energies, up to 12 eV, and compared the bands observed there to resonances revealed by the spectra of vibrational excitation cross sections. Dipole-allowed and dipole/spin forbidden electronic transitions in Fe(CO)(5)-relevant for neutral dissociation by electron impact-are probed using electron energy loss spectroscopy and time-dependent density functional theory calculations. Very good agreement between theory and experiment is obtained, permitting assignment of the observed bands.", publisher = "Royal Soc Chemistry, Cambridge", journal = "Physical Chemistry Chemical Physics", title = "Dissociative electron attachment and electronic excitation in Fe(CO)(5)", volume = "20", number = "17", pages = "11692-11701", doi = "10.1039/c8cp01387j" }
Allan, M., Lacko, M., Papp, P., Matejcik, S., Zlatar, M., Fabrikant, I. I., Kocisek, J.,& Fedor, J.. (2018). Dissociative electron attachment and electronic excitation in Fe(CO)(5). in Physical Chemistry Chemical Physics Royal Soc Chemistry, Cambridge., 20(17), 11692-11701. https://doi.org/10.1039/c8cp01387j
Allan M, Lacko M, Papp P, Matejcik S, Zlatar M, Fabrikant II, Kocisek J, Fedor J. Dissociative electron attachment and electronic excitation in Fe(CO)(5). in Physical Chemistry Chemical Physics. 2018;20(17):11692-11701. doi:10.1039/c8cp01387j .
Allan, Michael, Lacko, M., Papp, P., Matejcik, S., Zlatar, Matija, Fabrikant, I. I., Kocisek, J., Fedor, Juraj, "Dissociative electron attachment and electronic excitation in Fe(CO)(5)" in Physical Chemistry Chemical Physics, 20, no. 17 (2018):11692-11701, https://doi.org/10.1039/c8cp01387j . .