Autoionization Branching Ratios for Metal Halide Molecules Jeffrey J. Kay Lawrence Livermore National Laboratory OSU Molecular Spectroscopy Symposium Session RD (Spectroscopic Perturbations) 23 June 2011 Robert W. Field Massachusetts Institute of Technology
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Autoionization Branching Ratios for Metal Halide Molecules Jeffrey J. Kay Lawrence Livermore National Laboratory Jeffrey J. Kay Lawrence Livermore National.
Vibrational Autoionization of MX Rydberg States Formation of MX + Ions in Selected Rovibronic States?
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Autoionization Branching Ratios for Metal Halide Molecules
Jeffrey J. KayLawrence Livermore National Laboratory
OSU Molecular Spectroscopy SymposiumSession RD (Spectroscopic Perturbations)
23 June 2011
Robert W. FieldMassachusetts Institute of Technology
Cold MoleculesCurrently there is great interest in producing dense
samples of cold molecules and ions
Low velocities, long interaction times allow investigation of unexplored areas of molecular physics:
Cold Chemistry
Control UsingExternal Fields
Precision Spectroscopic Measurements
Time Variation of mp/me, Ammonia
New States of Matter
Quantum Degeneracy
Vibrational Autoionization of MX Rydberg States
Formation of MX+ Ions in Selected Rovibronic States?
Producing MX+ by Autoionization
Most ionization methods non-state-selective
Electron bombardmentNonresonant photoionization
What about autoionization?Specific rovibronic MX Rydberg levels can be selected by laser and spontaneously eject an electron, leaving behind MX+ ion.
What is the MX+ rovibrational state distribution? MX X 2S+1ΛΩ
MXIntermediate
State
MX Rydberg State
|n,L,Λ,v,J>
MX+ + e-
IonizationContinua
J+=0 J+=1J+=2
J+=3
Production of state-selected metal halide ions?
Autoionization Branching RatiosProduct state distributions following autoionization difficult to calculate.
MX n, l ,λ,v, J → e− e,λ + MX + v+, J+
MX+ rovibronic state distribution depends sensitively on electron-ion electrostatic interactions, especially their dependence on R
The only molecule with accurate and complete predictions of autoionization rovibronic branching ratios:
H2
One state 60+ decay channels!
Quantum Defect Model for CaFRecently, we developed a complete quantum defect theory (QDT) model for CaF
Summarizes electron-ion interactions in terms of an R-, E-dependent quantum defect matrix, μ(R, E)
75 parameter model = Infinite # of Rydberg statesVibronic perturbations