Fluorescence spectroscopy of jet- cooled phenylvinylacetylene in its ground and first excited states Speaker: Ching-Ping Liu Coworkers: Josh Newby and.

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Presentation transcript:

Fluorescence spectroscopy of jet- cooled phenylvinylacetylene in its ground and first excited states Speaker: Ching-Ping Liu Coworkers: Josh Newby and Christian Müller Advisor: Dr. Timothy Zwier Department of Chemistry, Purdue University

Motivation (1)Completing a series: (2) Structural isomerization: (3) C 10 H 8 isomers: Alternatives to naphthalene in combustion, planetary atmospheres? Previous detection: C 4 H 2 * + styrene, no spectral analysis 1-phenyl-1,3-butadiene Sharp UV spectrum phenylvinylacetylenephenyldiacetylene Broad UV spectrum Z-form E-form

Experiment Laser beam Collection mirrors Collimating lens To optics Housing Supersonic expansion Fluorescence excitationDispersed fluorescence PMT Monochromator / CCD

Fluorescence excitation spectrum of PVA

Single vibrational level dispersed fluorescence spectrum with the excitation of the origin band. Torsional progression C s symmetry a (in plane) modes: a  (out of plane) modes:  48 Obs / cm  

Excite 222 cm -1 Excite 254 cm -1 Excite 266 cm -1 Excite 326 cm -1 Excite 334 cm -1 Excite 400 cm -1 Part of the FE spectra SVLF spectra

FE spectra with various backing pressure of the carrier gases. (a) He 15 psi, and (b) He 40 psi, and (c) He 80 psi. (a) (b) (c) Clusters Cold band Hot bands v  =0 v  =1 v=0 v=1 v=2 v=3 S1S1 S0S

- 21 cm cm cm cm cm -1 Single vibrational level dispersed fluorescence spectra of hot bands. From v 47  =1 From v 48  =1 Duschinsky mixing

+ 191 cm cm cm cm -1 SVLF spectra with excitation involving the out-of-plane modes.

+ 104 cm cm cm cm -1 SVLF spectra with excitation involving the in-plane modes.

+ 931 cm cm cm cm cm cm cm cm -1 Single vibrational level dispersed fluorescence spectra.

Molecule S0S0 S1S1 S0S0 S1S1 S0S0 S1S1 S0S0 S1S1 S0S0 S1S1 Styrene trans-  -methylstyrene Phenylvinylacetylene Alkylbenzene     Table. Comparison of the vibrational frequencies of the benzene-type modes. R R R (6b) R (1) (12) (18a) (13) R R: substituent

Fluorescence excitation spectrum of phenylvinlyacetylene Warm condition Hot bands

1C-R2PI and hole-burning spectra Conformer or isomer A Conformer or isomer B Hole-burn Probe S0S0 S1S1 S0S0 S1S1 R2PI UVHB

+ 260 cm -1 band ? The SVLF spectrum with the excitation in the unknown band. Benzene-type modes

Conclusion The analysis and assignments of the ground and first excited states of phenylvinylacetylene are reported. The spectroscopy reveals Duschinsky mixing with four lower- frequency out-of-plane modes and IVR at high excess energy. The unknown band at 260 cm -1 above the origin in FE spectrum is probably originated from the Z isomer. Future work 1.Quantitatively analyze Duschinsky mixing with four low- frequency out-of-plane modes. 2.Synthesize the Z isomer to get the spectral information for comparison with the E isomer. 3.UV-induced structural isomerization of E- or Z-PVA.

Acknowledgement Advisor: Dr. Timothy Zwier Group members: Dr. Christian Müller* Dr. Jasper Clarkson Esteban Baquero Alvin Shubert Nathan Pillsbury Tracy LeGreve Josh Newby* Chirantha Rodrigo Josh Sebree Dr. Daniel Lee Funding: Taiwan Merit scholarship