Photoionization of the I 4d and valence orbitals of methyl iodide

Forbes, Ruaridh; De Fanis, Alberto; Rolles, Daniel; Pratt, Stephen T.; Powis, Ivan; Besley, Nicholas A.; Milosavljević, Aleksandar R.; Nicolas, Christophe; Bozek, John D; Holland, David M. P.

doi:10.1088/1361-6455/ab8c5a

Title: Photoionization of the I 4d and valence orbitals of methyl iodide

Journal Article · Thu Jun 25 00:00:00 EDT 2020 · Journal of Physics. B, Atomic, Molecular and Optical Physics

DOI:https://doi.org/10.1088/1361-6455/ab8c5a· OSTI ID:1646792

Forbes, Ruaridh ^[1]; De Fanis, Alberto ^[2]; Rolles, Daniel ^[3];

^[4];

^[5]; Besley, Nicholas A. ^[5]; Milosavljević, Aleksandar R. ^[6]; Nicolas, Christophe ^[6];

^[6];

^[7]

Univ. of College London (United Kingdom); Univ. of Ottawa, ON (Canada); SLAC National Accelerator Lab., Menlo Park, CA (United States)
European XFEL, Schenefeld (Germany)
Kansas State Univ., Manhattan, KS (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Nottingham (United Kingdom)
Synchrotron SOLEIL, Gif-sur-Yvette (France)
Daresbury Lab., Cheshire (United Kingdom)

Here, the photoabsorption and photoionization dynamics of the I 4d and valence orbitals in methyl iodide have been studied both experimentally and theoretically. Synchrotron radiation has been employed to measure the total ion yield in the vicinity of the I 4d ionization thresholds. The observed structure, due to excitations into Rydberg or valence states, has been assigned using transition energies and relative intensities computed with time-dependent density functional theory within the Tamm–Dancoff approximation. Photoelectron spectra, recorded with plane polarized radiation in two polarization geometries, have allowed the effect of autoionization on the valence electron angular distributions to be investigated. The spectra obtained at photon energies of 50.62 and 52.34 eV, coinciding respectively with the I 4d_5/2 → σ* and 4d_3/2 → σ* transitions, reveal, in addition to valence shell photoelectron bands, features not associated with simple photoionization of the parent molecule. High resolution photoelectron spectra of the I 4d main-lines display structure resulting from spin–orbit coupling and molecular field splitting. The binding energies of the five states contributing to the (I 4d)^-1 ionization have been determined. The iodine (in CH₃I) N₄₅VV Auger spectrum has been measured and the observed structure has been assigned using the core hole binding energies derived in the present work together with established ionization energies of the doubly charged ion. The experimentally determined Auger electron angular distributions have been discussed in relation to the theoretical angular distribution parameter characterizing the spatial alignment of molecular axes in the (I 4d)^-1 state.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC); Science and Technology Facilities Council (STFC)

Grant/Contract Number:: AC02-76SF00515; AC02-06CH11357; FG02-86ER13491; EP/N002148/1

OSTI ID:: 1646792

Alternate ID(s):: OSTI ID: 1660713

Journal Information:: Journal of Physics. B, Atomic, Molecular and Optical Physics, Vol. 53, Issue 15; ISSN 0953-4075

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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