Energy Transfer Dynamics in the

A(0u+) State of Bi2               

Joseph L. Cox
Michael W. Dolezal
Robert E Franklin
Glen P. Perram

Department of Engineering Physics

Air Force Institute of Technology
Wright-Patterson Air Force Base, OH
 Bismuth Potential Energy Curves

The Bi2 A(0u+) State:

Small Vibrational Spacing -

e =132.403 cm-1

Low Anharmonicity -
e e / e=0.0024

Large Moment of Inertia -

Bv = 0.019739 cm-1
Laser Induced Fluorescence Experiments          

Steady-State (V-T, R-T) Pulsed (Lifetime, Quenching)

Laser Excitation Spectrum (CW)         

Residuals of the v'' = 3 to v' = 3 Vibrational Band

Current Work
0
observed - predicted (cm )
-1

-1

Gerber

-2
-200 -150 -100 -50 0 50 100 150 200  J Molecular Spectroscopy, 194, 1 (1999).
Rotational Number (m)
Laser Excitation Spectrum (Pulsed)          

Predissociation
Pulsed Lifetime Studies  

I (t )  I o e  t   o  k Q [ M ]

v’=21, J’=50 (100 mTorr)

Predissociation Rates

o  r  k pd (v) J ( J  1)
Electronic Quenching Rates

I (t )  I o e  t   o  k Q [ M ]

v’=18-21

v’=23

v’=22
 Vibrational Energy Transfer Rates
Nv kVT (vo  v )[M ] / r

N vo N 
1  [kQ (v)[M ]   kVT (v  w)][ M ] / r   kVT ( w  v)  w  [ M ] / r
w  Nv 

Nv Ax

N vo 1  Bx
V-T Rates

J Chem Phys, 111, 5757 (1999).

Gas v o’ kVT(vv-1) kVT(10) v(1,0) / g

He 2 10.6  1.5 5.3  0.7 0.0075

Ne 1-4 (see Table I) 4.8  0.9 0.0142

Ar 3 7.6  1.2 2.5  0.4 0.0089

Kr 2 4.8  0.7 2.4  0.4 0.0112

Xe 2 6.8  1.3 3.4  0.7 0.0175

Vibrational Energy Transfer Rates

 (1,0)  '   ' 

1/ 6   ' 
1/ 3
     
P(1,0) M    exp  3/2      
g   T   T
   2T   kT  

'4 2 L2 (2c e ) 2  / kT
hc e / kT
() Bi2(A) (present work)
(O) Br2(B)
() BrCl(B)
() BrF(B)
() IF(B)

=ceL(/8kT/)1/2
Rotational Energy Transfer Rates
Rotational Energy Transfer Rates

State-to-state rotational energy transfer

rate constants for Ne after laser excitation
of v’=1, J’=201. Three scaling law fits
are also shown: () SPG1, (….) SPG2
and (---) EGL1.
Conclusions

-Strong heterogeneous predissociation in Bi2(A) for v’>22

-- no stable levels above v’
-Rapid electronic quenching independent of v’ until predissociation
-Rapid V-T transfer, but less than predicted by SSH theory
-- linear scaling with v’
-- no significant multi-quantum transfer
-R-T transfer best characterized by a statistical power gap sclaing
law with change in rotational state per collision as large as 52
-- angular momentum based scaling laws statistically inferior