Re-analysis of the dispersed fluorescence spectra of the C 3 -rare gas atom complexes Yi-Jen Wang, Anthony J. Merer, Yen-Chu Hsu 王意禎，米安東，許艷珠 IAMS, Academia Sinica Taipei, Taiwan, R. O. C. Ministry of Science and Technology, R. O. C.

Electronic transitions of C 3 X1+gX1+g ~ A1uA1u ~ 4050 Ǻ Comet system (24676 cm  ) 6483 cm  1 (IR emission) b3gb3g ~ 1+u1+u nm system Vacuum ultraviolet system C1gC1g ~ D1gD1g ~ cm  1 (Neon matrix) Double resonance            a3ua3u ~ Low bending frequency ～ 63 cm -1

C 3 Ar ( ) Structure of C 3 Ar Estimations from our rotational analysis: R″( )=3.81Å, ∠ C-C-C = º R′ (Ã )=3.7 5 Å, Ar MCTDH

Predissociation and Binding Energy Determination 1.Spectral broadening only observed in 2 bands of C 3 Ne, because Doppler broadening is our major problem. 2.Lifetime shortening i.e. Ar-SH, Kr-SH (Applegate et.al., J. Chem. Phys. (1998); Yang et. al. J. Chem. Phys. (1993)) The fluorescence lifetimes of the pure C 3 -bending levels of the A state vary very little. (J. Phys. Chem. A, 117, (2013).) So are those of the Rg complex. 3.Detection of Fragment a. Dispersed fluorescence, i.e. Ne, Ar, Kr-OH/SH b. LIF, i.e. Ar-OH c. Velocity mapping, i.e. (H 2 O) 2 (Rocher-Caserline et. al. (2011) x x x x

Binding energy and Product channels (D 0 ″ +ΔE 1 - ΔE 2 ) < ΔE 3

K= Λ (Electroinc orbital angular momentum) ± ℓ ( vibrational angular momentum ) + upper Renner comp. – lower Renner comp.

Experiment C 3 molecules were generated by photolyzing allene with 193nm laser light at the tip of a nozzle. A 30μm x3mm slit was used to increase the optical path length and reduce the Doppler width. Emission spectra Old data: (J. Chem. Phys. (2004, 2011)) 0.3 m-monochromator + OMA detector gated fluorescence: first 1µs Spectral resolution ≥ 12 cm -1. New data: 0.5 m-monochromator + ICCD detector gated signals: first 50ns –first 400 ns Spectral resolution ≥ 6.6 cm -1.

Emission Spectra of C 3 -Xe, b , Δ g (-84 cm -1 ) 1 -,Σ g ((-227.3) 0,Π u (-364) - -v ”=0,2,4, 6 Observed C 3 (A) product states Binding energy < D o ”<329.1 cm -1

Emission Spectra of C 3 Ar, b 0 2- K 0 1 Observed C 3 (A) product states 1, Δ g (-84 cm -1 ) 1 -,Σ g ((-227.3) 0,Π u (-364) -v”=1,3,5,7 v”=0,2,4,6 Binding energy 73.7<D o ” (C 3 Ar)<217 cm -1 Similar product channels observed at C 3 Kr, b 0 2- K 0 1, 61.6< D o ” (C 3 Kr)<204.9cm -1

Observed C 3 fragment channels at b 0 4- K ,Δ g 3 -, Σ g 2-,Φu 2-,Φu 2 -,Π u 1 +,Σ g 1,Δ g 1 -,Σ g 0, Π u D 0 ”( cm -1 ) ΔE 3 (cm -1 ) C 3 Ne v”=1,3, 5,7,9 v”=2,4, 6,8 v”=0,2, 4, <152 C , v”=1,3, 5,7,9 v”=2,4, 6,8 - v”=1,3, 5, <141 C v”=0,2, 4,6 -v”=1,3, 5 v”=1,3v”=0,2 <185 C 3 Kr - v”=1,3, 5,7, 9 v”=2,4, 6,8 v”=2,4, 6 v”=1,3, 5 v”=1,5v”=1,3 -<190 C 3 Xe - - v”=2,4, 8 (blend ed) v”=2,4, 6 v”=1,3, 5,7 v”=1,3, 5 v”=1,3v”=0,2 <

Observed C 3 fragment channels at b 0 2+ K ,Πu4-,Πu 3-,Δg3-,Δg 3-,Σg3-,Σg 2-,Φu2-,Φu 2-,Πu2-,Πu 1 +, Σ g 1, Δ g 1 -, Σ g 0, Π u D 0 ” ΔE 3 (cm -1 ) C 3 Ne v”=2,4,6,8,10 v”=1, 3,5, <79 C 3 Ar - v”=1, 3,5,7, 9,11 v”=2,4,6,8,10 -v”=1,3, <231 C 3 Kr - v”=1, 3,5,7, 9 v”=1,3,5 v”=2,4,6,8 v”=0,2,4,6 v”=1,3,5 - -<223 C 3 Xe - v”=1, 3,9 v”=1,3,5,7 v”=2,4,6 v”=0,2,4,6 v”=1,3,5,7 v”=1,3,5 v”=1,3v”=0,2 <223

Observation of different branching ratios of 3 -, Δ g to 3 -, Σ g within 2 cm -1 excitation energies. Emission Spectra of C 3 Ne, b 0 4- K o 1

Observation of vibraional relaxation by cm -1 prior VP Emission Spectra of C 3 Ne, b 0 2+ K o 1

Emission spectra of C 3 Ar, b 0 2+ K 0 1 Observation of vibrational relaxation of 16 cm -1 prior VP.

cm cm -1

Conclusions 1.Our preliminary results showed that the binding energies of C 3 Rg are D 0 ”(C 3 Ne) < 79 cm -1, 73.7< D 0 ”(C 3 Ar) < 141 cm < D 0 ”(C 3 Kr) < 190 cm < D 0 ”(C 3 Xe) < cm -1 2.Evidences of strong Coriolis couplings between type A and type C bands, which were found in the rotational analysis of the excitation spectra of C 3 Ar, are also observed in their emission spectra. However, this is not so with cold rotational temperature of C 3 Ne. Rotational temperature effect observed on the emission spectra of C 3 Ne, b 0 2- K 0 1 suggested that by warming the rotational temperature the Coriolis coupling could be enhanced. 3.Most of the bands we reported here showed that as soon as a new vibrational predissociation channel is opened, bands lie above it would relax by cm -1 prior the vibrational predissociation. Since the vibrational relaxation is not fast enough so that the complex also has a chance to fluorescence. We tentatively assign this cm -1 as two quanta of vdW bending or vibrational frequency difference between C 3 in-plane bending and out-of-plane bending vibrations. 4.Propensity rules of vibrational predissociation are, Δv= , ΔK=0, ±1, ±2, ±3. But “Resonance” is the key.

No vibrational relaxation processes were observed at and cm -1. Different branching ratios of 3 -, Δ g /3 -, Σ g also observed at these two excited levels. cm -1