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Multiphoton ionization of SiH3 and SiD3 radicals: Electronic spectra, vibrational analyses of the ground and Rydberg states, and ionization potentials

J. Chem. Phys. 91, 3340 (1989); doi:10.1063/1.456909

Issue Date: 15 September 1989

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Russell D. Johnson III, Bilin P. Tsai, and Jeffrey W. Hudgens
Chemical Kinetics Division, Center for Chemical Technology, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
The electronic spectra of silyl radicals, SiH3 and SiD3, were observed between 310 and 430 nm (46 000–64 000 cm−1) by resonance enhanced multiphoton ionization (REMPI) mass spectroscopy. The spectra were generated through a 2+1 REMPI mechanism. Two Rydberg series originating from planar, D3h point group states were observed. One series, of quantum defect delta=1.45(2), is comprised of the E-tilde 2A<sup>[script `]</sup><sub>2</sub>(4p), J-tilde 2A[script `]2(5p), and M-tilde 2A[script `]2(6p) Rydberg states which have origins at nu0–0 =48 438, 56 929, and 60 341 cm−1 in SiH3 and at nu0–0 =48 391, 56 874, and 60 267 cm−1 in SiD3. In SiD3 theP-tilde 2A[script `]2(7p) Rydberg origin was observed at nu0–0 =62 002 cm−1. The H-tilde, K-tilde, and N-tilde states observed in the SiD3 spectrum comprise the second Rydberg series, delta=2.09, and were tentatively assigned as ns 2A<sup>[script ']</sup><sub>1</sub> Rydberg states (n=5, 6, 7). The K-tilde and N-tilde origins were observed at nu0–0 =58 417 and 61 005 cm−1. A fit of the Rydberg formula to the np 2A[script `]2(n>=5) origins found the adiabatic ionization potential of the SiH3 and SiD3 radicals to be IPa=8.135(+5,−2) eV and IPa=8.128(1) eV, respectively. Detailed vibrational analyses of these Rydberg states are presented. Analysis showed that in the E-tilde 2A<sup>[script `]</sup><sub>2</sub> (4p) state of the SiH3 radical omega<sup></sup><sub>2</sub> (a<sup>[script `]</sup><sub>2</sub> symmetric bend)=796(7) and 2omega<sup></sup><sub>4</sub> /2(e[script '] degenerate bend)=870(5) cm−1 and that in SiD3 radical omega<sup>[script ']</sup><sub>1</sub> (a<sup></sup><sub>1</sub> SiH3 symmetric stretch)=1576(3), omega<sup>[script ']</sup><sub>2</sub> =589(3), and 2omega<sup></sup><sub>4</sub> /2=635(6) cm−1. The REMPI spectra exhibited nu<sup>[script `]</sup><sub>2</sub> hot bands from vibrational levels as high as Ev =2073 cm−1 in the X-tilde 2A1state. Modeling calculations, which fit the numerous nu[script `]2 hot bands, predicted barriers to inversion of Binv=1935 cm−1 and Binv =1925 cm−1 for SiH3 and SiD3 X-tilde 2A1 radicals, respectively. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 3 April 1989; accepted 8 June 1989
Permalink: http://link.aip.org/link/?JCPSA6/91/3340/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.80.Rv
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states)
  • 35.20.Wg
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Mass spectra
  • 35.20.Pa
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Rotation, vibration, and vibrationrotation constants
  • 35.20.Vf
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Ionization potentials, electron affinities, molecular core binding energy
  • YEAR: 1988-89

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (48)
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