2
3 With UV irradiation: Cl 2 + h 2 Cl* Cl* + H 2 (v = 0) HCl + H Cl* + matrix Cl Cl + H 2 (v = 0) no reaction With IR irradiation: H 2 (v = 0) H 2 (v = 1) Cl + H 2 (v = 1) HCl + H 360 cm 1
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6 J. Phys. Chem. A 113, 7621 (2009)
7 = =
Previous work on Cl + H 2 (Anderson) A few questions explored with a tunable IR laser: Spectroscopy of Cl-H 2 Efficiencies in excitation at various bands of H 2 Is H 2 (v = 1) delocalized? Formation of HCl vs. (HCl) 2 Reactivity of Cl* 8
9 Nd:YAG Laser He-Ne MCT 3 K target Photoacoustic Cell T=95% BS 2000 3100 cm 1 filter 4000 cm 1 cutoff filter FTIR Globar source power meter H2H sccm 5.00 sccm Cl 2 12 K pH 2 converter IR OPO/OPA Laser frequency scanning from 4000 cm 1 up HCl-increase Scan IR laser frequency 365 nm LED or 355 nm Laser
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11 IR laser pumping from 4135 cm - 1 upward
12 A. After 365 nm for 2 h B. HCl action spectrum A B
cm cm -1 HCl increase / a.u IR intensity / a.u Laser energy / mJ pulse (*6 min)5.1 (*20 min) Relative Efficiency Frequency bandwidth =1.3 cm -1 x3
IR laser at cm - 1 IR laser at cm - nm FTIR probe IR laser pump 14 IR bandwidth =0.25 cm -1 3 min 6 min
15 (HCl) n (HCl) 2 (HCl) 3 IR laser frequency bandwidth =0.25 cm -1 AB C After 365 nm for 2 hour
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17 Time 4230 cm nm overlapIR before uv pulsesUV before IR pulses 4230 cm nm
The spectrum of Cl-induced Q 1 (0) and S 1 (0) lines are identified near / and cm 1. Excitation of the Cl-induced Q 1 (0) line has an efficiency ~2 times that of the Q R (0) band. Excitation of the Q R (0) band is delocalized. Excitation of the Q R (0) band produced more dimers than excitation of the Cl-induced Q 1 (0) line. Q 1 (0) + S 1 (0) less efficient? (more work) How long do the vibrons survive? (more work) 18
Jen-Yu Wu Mohammed Bahou 19