Jh. Reho et al., Photoinduced nonadiabatic dynamics in quartet Na-3 and K-3 formed using helium nanodroplet isolation, J CHEM PHYS, 115(22), 2001, pp. 10265-10274
Helium nanodroplet isolation is used to produce van der Waals-bound quartet
state alkali trimers (Na-3 and K-3) selectively over the corresponding che
mically bound doublet trimers. Frequency-resolved excitation and emission s
pectroscopy reveals the presence of nonadiabatic spin-flip processes in the
electronically excited states. A total of four quartet to quartet electron
ic transitions are observed: the 2 E-4('),1 E-4<--1 (4)A(2)(') transitions
of Na-3 and the 1 (4)A(1)('),2 E-4(')<--1 (4)A(2)(') transitions of K-3. Ti
me-resolved spectroscopy reveals that intersystem crossing times in Na-3 de
crease from 1.4 ns after excitation of the 0-0 band to approximately 400 ps
for the higher vibronic levels (3,5/2). Analysis of the resonant quartet f
luorescence reveals that the excited electronic state cools vibrationally o
n a time scale that is comparable to, but slower than, the intersystem cros
sing time. (C) 2001 American Institute of Physics.