Spectroscopic and Kinetic Studies of Bismuth Dimers

Robert Eugene Franklin


The spectroscopy of high rotational levels (J <= 211) in Bi2 X(Og(+)) and A(Ou(+)) was investigated for 2<=v"<=5 and 0<=v'<=4 by observing total fluorescence from laser excitation. Dunham coefficients were derived that fit all observed rotational lines to within 0.01 /cm. Franck-Condon factors were calculated and experimentally verified for transitions originating from the initially populated levels 0<=v'<=5. Vibrational energy transfer upon collision with rare gas collision partners was investigated for the low-lying vibrational levels of the A-state using spectrally resolved, continuous wave laser induced fluorescence. Vibrational transfer was adequately modeled by Landau-Teller scaling of the deltav=-1 vibrational transfer rates with fundamental rate coefficients ranging from kv=5.29x10(exp -12) cu cm/molec-sec for collisions with helium to 2.38x10(exp -12) cu cm/molec-sec for krypton. Electronic quenching and multi-quantum transfer rates were approximately an order of magnitude slower than single quantum transfer rates.