Vacuum ultraviolet pulsed field ionization-photoelectron and infrared-photoinduced Rydberg ionization study of trans-1,3-butadiene.
The vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) spectrum of trans-1,3-butadiene (trans-CH(2)[Double Bond]CHCH[Double Bond]CH(2)) has been measured in the region of 0-1700 cm(-1) above its ionization energy (IE) to probe the vibrational modes nu(i) (+) (i=1-18) of trans-CH(2)[Double Bond]CHCH[Double Bond]CH(2) (+). The high-frequency vibrational modes nu(i) (+) (i=19, 22, and 23) of trans-CH(2)[Double Bond]CHCH[Double Bond]CH(2) (+) 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-CH(2)[Double Bond]CHCH[Double Bond]CH(2)) 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-CH(2)[Double Bond]CHCH[Double Bond]CH(2) (+) have been determined, including nu(1) (+)=182+/-3, nu(2) (+)=300+/-3, nu(3) (+)=428+/-3, nu(4) (+)=514+/-3, nu(5) (+)=554+/-5, nu(6) (+)=901+/-3, nu(7) (+)=928+/-5, nu(8) (+)=994+/-3, nu(9) (+)=1008+/-5, nu(10) (+)=1094+/-5, nu(13) (+)=1258+/-3, nu(14) (+)=1293+/-3, nu(16) (+)=1479+/-3, nu(18) (+)=1620+/-3, nu(19) (+)=2985+/-10, nu(22) (+)=3030+/-10, and nu(23) (+)=3105+/-10 cm(-1).
Hou
Y
Y
Department of Chemistry, University of California, Davis, Davis, California 95616, USA.
Woo
H-K
HK
Wang
P
P
Xing
X
X
Ng
C Y
CY
Lau
K-C
KC
D002070:Butadienes / Q000737:chemistry* / Q000528:radiation effects*; D004583:Electrons; D007259:Infrared Rays; D008958:Models, Molecular; D013057:Spectrum Analysis; D013237:Stereoisomerism; D014466:Ultraviolet Rays; D014732:Vibration
D002070:Butadienes; C031763:1,3-butadiene