@article{ea8bd5e8f2a842a5aa4eef7f953596f5,
title = "Boron 1s photoelectron spectrum of 11BF3: Vibrational structure and linewidth",
abstract = "The boron 1s photoelectron spectrum of B11 F3 has been measured at a photon energy of 400 eV and a resolution of about 55 meV. The pronounced vibrational structure seen in the spectrum has been analyzed to give the harmonic and anharmonic vibrational frequencies of the symmetric stretching mode, 128.1 and 0.15 meV, as well as the change in equilibrium BF bond length upon ionization, -5.83 pm. A similar change in bond length has been observed for P F3 and Si F4, but a much smaller change for C F4. Theoretical calculations for B F3 that include the effects of electron correlation give results that are in reasonable accord with the experimental values. The Lorentzian (lifetime) width of the boron 1s core hole in B F3 is found to be 72 meV, comparable to the value of 77 meV that has been reported for C F4.",
author = "Thomas, {T. Darrah} and Ralph P{\"u}ttner and Hironobu Fukuzawa and Georg Pr{\"u}mper and Kiyoshi Ueda and Edwin Kukk and Rami Sankari and James Harries and Yusuke Tamenori and Takahiro Tanaka and Masamitsu Hoshino and Hiroshi Tanaka",
note = "Funding Information: We thank Knut B{\o}rve for his advice on appropriate basis sets for the theoretical calculations. This research was carried out with the approval of JASRI (Proposal No. 2007A1046) and was supported in part by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy and by grants in aid for scientific research provided by the Japan Society for Promotion of Science (JSPS). E.K. and R.S. acknowledge financial support from the Academy of Finland and R.P. from a JSPS fellowship. Table I. Harmonic and anharmonic frequencies for the symmetric stretching mode in boron 1 s ionized B 11 F 3 . Change in BF equilibrium bond length upon ionization. Derived values of Gaussian and Lorentzian components of the linewidth. Figures in parentheses indicate the uncertainty in the last digit. Pass energy(eV) Gaussian(meV) Lorentzian(meV) ω 1 (meV) x 11 (meV) Δ R (pm) Expt. Free fit 20 60 72 128.6(8) − 0.21 ( 12 ) − 5.6 Free fit, recoil included 20 56 72 128.2(8) − 0.13 ( 13 ) − 5.6 Morse-oscillator fit 20 61 72 128.1(1) − 0.15 ( 2 ) − 5.83 ( 5 ) Free fit 50 78 71 128.2(9) − 0.15 ( 14 ) − 5.6 Free fit, recoil included 50 75 70 128.1(9) − 0.12 ( 14 ) − 5.6 Theor. HF (harmonic) 142.3 − 6.83 B3LYP (harmonic) 129.5 − 6.14 B3LYP (Morse) 129.7 − 0.18 − 6.14 CCSD(T) (harmonic) 129.7 − 6.08 Table II. Harmonic and anharmonic frequencies for the symmetric stretching mode in silicon- 2 p ionized Si F 4 . Changes in SiF and PF equilibrium bond lengths upon ionization. Figures in parentheses indicate the uncertainty in the last digit. Results for P F 3 are from Ref. 9 . ω 1 (eV) x 11 neutral(meV) x 11 ion(meV) Δ R (pm) Si F 4 Free fit 112.7(2) − 0.11 ( 3 ) − 5.73 Morse-oscillator fit − 0.12 − 0.15 − 6.04 P F 3 Free fit 122.2(4) − 0.18 ( 8 ) Morse-oscillator fit − 6.0 FIG. 1. Boron 1 s photoelectron spectrum of B 11 F 3 measured at a photon energy of 400 eV and an analyzer pass energy of 20 eV . Open circles show the data. The solid line shows a least-squares fit to the data obtained using a Morse-potential model. The vertical lines show the results of a fit with all intensities and positions as free parameters. The triangles show the intensities given by a harmonic-oscillator model. At both ends of the spectrum, the data and the fits extend 0.4 eV beyond the range shown. ",
year = "2007",
doi = "10.1063/1.2820772",
language = "English",
volume = "127",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "24",
}