history for NeI 2 (E, 0,n E = 0) complex lies at larger time than those for the v E = 1–3
groups (Fig. 6.24)
since the former is populated from the rather long-lived NeI 2 (E, 0, 0) complex
(s = 8 ns) and the latter from the short-lived one (s
2) ns (see below).
The VP channels (6.3.11) open for the NeI 2 (E,v E ! 1,n E ) complexes (see
Figs. 6.16, 6.19), and the complex decay becomes much faster. The origins of the
luminescence in the k lum % 3900–4400 Å spectral range are both VP products,
I 2 (E) (Dv E 6 ¼ 0 VP channel), and the complex (Dv E = 0 VP channel). Luminescence
of the complex or the VP products in this spectral range is simulated as luminescence from the optically populated ðv
max
E Þ or lower vibrational levels, respectively.
Simulations of the luminescence spectra show that the relative contribution of the
complex luminescence is estimated as * 6%. The branching ratio of VP increases
two times at NeI 2 (E,v E = 1,n E ) complex relative to that of NeI 2 (E,v E = 0,n E ) one, and
then decreases smoothly due to a competition of the VP and EP channels (see
Table 6.9). Assuming that the radiative decay rate of the complex, k 3.13 , depends
weakly on v E , one can estimate the rate of the VP channel, k 3.11 , as 5Á10
8 s
−1 .
Comparison of branching ratios of VP and EP channels gives k 3.12 % 5Á10
8 s
−1 ,
and lifetime of the NeI 2 (E,v E > 1,n E ) complex is < 1 ns, much less than that of the
NeI 2 (E,0,n E ) one (8 ns). Time-resolved measurements confirm that both I 2 (E,v E and
D,v D ) states are populated in these cases from the short-lived complex (Figs. 6.23,
Fig. 6.22 Experimental (solid line) and simulated (broken line) luminescence spectra in the
k lum = 2900–3550 Å and 4000–4400 Å spectral ranges at the v E = 0 band of the NeI 2 (E,v E ,
n E = 0 ← B,19,n B = 0) transitions. Spectral resolution, FWHM = 10 Å. Experimental spectrum is
offset for clarity. Populations of the D,v D and b,v b vibronic states are given in the inset. The k 2
laser line is marked [95] (Reprinted from Chemical Physics Letters, Vol. 696, V.V. Baturo, S.S.
Lukashov, S.A. Poretsky, A.M. Pravilov, Luminescence of the NeI 2 van der Waals complex., p.
p. 26-30 (2018) with permission from Elsevier)
232
6 Weakly-Bound Complexes and Clusters
groups (Fig. 6.24)
since the former is populated from the rather long-lived NeI 2 (E, 0, 0) complex
(s = 8 ns) and the latter from the short-lived one (s
2) ns (see below).
The VP channels (6.3.11) open for the NeI 2 (E,v E ! 1,n E ) complexes (see
Figs. 6.16, 6.19), and the complex decay becomes much faster. The origins of the
luminescence in the k lum % 3900–4400 Å spectral range are both VP products,
I 2 (E) (Dv E 6 ¼ 0 VP channel), and the complex (Dv E = 0 VP channel). Luminescence
of the complex or the VP products in this spectral range is simulated as luminescence from the optically populated ðv
max
E Þ or lower vibrational levels, respectively.
Simulations of the luminescence spectra show that the relative contribution of the
complex luminescence is estimated as * 6%. The branching ratio of VP increases
two times at NeI 2 (E,v E = 1,n E ) complex relative to that of NeI 2 (E,v E = 0,n E ) one, and
then decreases smoothly due to a competition of the VP and EP channels (see
Table 6.9). Assuming that the radiative decay rate of the complex, k 3.13 , depends
weakly on v E , one can estimate the rate of the VP channel, k 3.11 , as 5Á10
8 s
−1 .
Comparison of branching ratios of VP and EP channels gives k 3.12 % 5Á10
8 s
−1 ,
and lifetime of the NeI 2 (E,v E > 1,n E ) complex is < 1 ns, much less than that of the
NeI 2 (E,0,n E ) one (8 ns). Time-resolved measurements confirm that both I 2 (E,v E and
D,v D ) states are populated in these cases from the short-lived complex (Figs. 6.23,
Fig. 6.22 Experimental (solid line) and simulated (broken line) luminescence spectra in the
k lum = 2900–3550 Å and 4000–4400 Å spectral ranges at the v E = 0 band of the NeI 2 (E,v E ,
n E = 0 ← B,19,n B = 0) transitions. Spectral resolution, FWHM = 10 Å. Experimental spectrum is
offset for clarity. Populations of the D,v D and b,v b vibronic states are given in the inset. The k 2
laser line is marked [95] (Reprinted from Chemical Physics Letters, Vol. 696, V.V. Baturo, S.S.
Lukashov, S.A. Poretsky, A.M. Pravilov, Luminescence of the NeI 2 van der Waals complex., p.
p. 26-30 (2018) with permission from Elsevier)
232
6 Weakly-Bound Complexes and Clusters