STUDIES OF THE PREDISSOCIATED, QUASILINEAR STATE OF

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Presentation transcript:

STUDIES OF THE PREDISSOCIATED, QUASILINEAR STATE OF CH35Cl AND CD35Cl PROBED BY OPTICAL-OPTICAL DOUBLE RESONANCE SPECTROSCOPY Chong Tao, Calvin Mukarakate, Scott A. Reid Department of Chemistry, Marquette University 64rd International Symposium on Molecular Spectroscopy June 24th, 2009 WF01

Halocarbene photochemistry is largely unexplored Halocarbons (e.g., CFCs) have been famously implicated in stratospheric ozone depletion It is well established that halocarbenes are produced in the photodecomposition of halocarbons. To date, very little is known about the ultraviolet photochemistry of halocarbenes. Reid, El-Khoury, Tarnovsky, Ault

Mono- halocarbenes (CHX) S0 T1 S1 S2 S2 28000 24000 20000 S1 Energy in cm-1 16000 12000 8000 T1 4000 S0 CHF CHCl CHBr CHI

Singlet potential energy surfaces of CHF (CASSCF/cc-pVTZ) B1A’ C A1A” C X1A’ C

Schematic PES along C-X bond in :CXY Scott Kable and George Bacskay, Sydney

CASSCF calculations for CHCl Eric Brown, Loyola University

CASSCF calculations for CHCl B state ~ CASSCF(6,5)/cc-pVTZ

Stationary points on the CHCl PES ~ ~ ~ ~

Optical-optical double resonance spectroscopy HV G PUMP PROBE PMT Boxcar Probe Boxcar ADC Pump

OODR Spectroscopy of CHF SEP transitions All B state levels are broadened by dissociation B state is quasi-linear, levels labeled by (v1,v2ℓ,v3)

OODR Spectrum of CH35Cl CHCl (0,91,2) By exploiting various intermediate levels, transitions involving the C-H stretch (1 quantum) and C-Cl stretch (1-3 quanta) in combination with bend are observed All levels above ~ 26 000 cm-1 display lifetime broadening CHCl (0,91,2)

OODR Spectrum of CD35Cl CDCl (0,131,1) Linewidths are narrower than found in CHCl Many levels can be rotationally resolved The three line pattern at right reflects the ΔJ = 0, ±1 selection rule CDCl (0,131,1)

Vibrational frequencies for CHCl and CDCl in the B state ~ CH35Cl CD35Cl Vibration Exp. (cm-1) (cm-1)a ω1 3180 2450 ω2 737 574 ω3 960 961 ω3 in cm-1 for CH35Cl: X (812), A (926), B (960) ω1 in cm-1 for CH35Cl: X (2803), A (2980), B (3180)

Where is the electronic origin? Extrapolation predicts origin to lie near 20800 cm-1

Linewidth Data MP4/cc-pVTZ Energies C(3P) + HCl 25900 cm-1 (barrier) CCl(2Π) + H 29100 cm-1 (asymptote) CH(2Π) + Cl 33100 cm-1

Summary The state of CH35Cl and CD35Cl has been investigated with OODR spectroscopy The state is quasilinear, with a very small barrier. The electronic origin lies near 20,800 cm-1 At energies near 26,000 cm-1, the lines are broadened by a homogenous process (presumably dissociation) This is very close to the calculated barrier for elimination of HCl on the triplet surface

Acknowledgements People: Scott Kable Tim Schmidt George Bacskay Funding: National Science Foundation (CHE-0717960)