Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron and Infrared-Photoinduced Rydberg Ionization Study of trans-1,3-butadiene

Journal Article · Wed Sep 17 00:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2973635· OSTI ID:959173

Hou, Yu ^[1]; Woo, H. K. ^[1]; Wang, P. ^[1]; Xing, X. ^[1]; Ng, Cheuk-Yiu ^[1]; Lau, Kai Chung ^[2]

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1. Univ. of California, Davis, CA (United States)
2. City Univ. of Hong Kong (China)

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) spectrum of trans-1,3-butadiene (trans-CH₂==CHCH==CH₂⁺) has been measured in the region of 0–1700 cm^-1 above its ionization energy (IE) to probe the vibrational modes v_i ⁺ (i=1–18) of trans-CH₂==CHCH==CH₂ ⁺. The high-frequency vibrational modes v_i ⁺ (i=19, 22, and 23) of trans-CH₂==CHCH==CH₂ ⁺ have also been probed by the VUV-infrared-photoinduced Rydberg ionization (VUV-IR-PIRI) measurement. On the basis of the semiempirical simulation of the origin VUV-PFI-PE band, the IE(trans-CH₂==CHCH==CH₂) is determined to be 73 150.1±1.5 cm^-1 (9.06946±0.00019 eV). This value has been used to benchmark the state-of-the-art theoretical IE prediction based on the CCSD(T,Full)/CBS procedures, the calculation of which is reported in the present study. The vibrational bands observed in the VUV-PFI-PE and VUV-IR-PIRI spectra were assigned based on ab initio anharmonic vibrational frequencies and Franck–Condon factor calculations for the photoionization transitions. Combining the VUV-PFI-PE and VUV-IR-PIRI measurements, 17 fundamental vibrational frequencies of trans-CH₂==CHCH==CH₂ ⁺ have been determined, including v₁ ⁺=182±3, v₂ ⁺=300±3, v₃ ⁺=428±3, v₄ ⁺=514±3, v₅ ⁺=554±5, v₆ ⁺ =901±3, v₇ ⁺=928±5, v₈ ⁺=994±3, v₉ ⁺=1008±5, v₁₀ ⁺ =1094±5, v₁₃ ⁺ =1258±3, v₁₄ + =1293±3, v₁₆ ⁺ =1479±3, v₁₈ ⁺ =1620±3, v₁₉ ⁺ =2985±10, v₂₂ ⁺ =3030±10, and v₂₃ ⁺ =3105±10 cm^-1.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 959173
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 129; ISSN JCPSA6; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DATA
DIENES
EXTREME ULTRAVIOLET SPECTRA
Environmental Molecular Sciences Laboratory
INFRARED SPECTRA
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
VIBRATIONAL STATES