R. Zadoyan et al., DYNAMICAL SPECTROSCOPY OF MANY-BODY INTERACTIONS COHERENT VIBRATIONS AND PREDISSOCIATION OF I-2(B) IN SOLID KR, Journal of the Chemical Society. Faraday transactions, 92(11), 1996, pp. 1821-1829
Citations number
104
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
I-2(B) isolated in Kr matrices is prepared between 560 and 490 nm, and
probed via the f(0(g)(+)) <-- B(0(n)(+)) transition, with a time reso
lution of 150-200 fs. It is shown that the prepared vibrational popula
tion evolves coherently and decays in amplitude owing to predissociati
on. Where the population is prepared on a single electronic surface, n
ear lambda = 550 nm, the experimental signal can be reproduced quantit
atively via classical simulations. The analysis yields: (a) the locati
on of the f(0(g)(+)) ion-pair state, the electronic solvation energy o
f which the Kr is determined as 4300 cm(-1), (b) the characterization
of vibrational relaxation dynamics, which near upsilon = 20 reaches a
limiting decay rate of 60 cm(-1) per period and (c) a direct measureme
nt of the host-induced electronic predissociation lifetime of 4.5 ps.
With the assumption that this is due to B --> a curve crossing, an ele
ctronic matrix element of 54 +/- 7 cm(-1) is implied in solid Kr. The
solid-state results are discussed in relation to measurements in other
phases: gas, liquid and clusters. The example is used as an illustrat
ion of dynamical spectroscopy, as time-dependent resonances which can
be interpreted through analysis of the underlying many-body dynamics.