Geoscience Reference
In-Depth Information
(
I
X
is the ionization potential of the X atom) permits us to rewrite Eq.
1.39
as E
k
C
E
>I
X
. Assuming that the difference I
X
E
1
D
2n
2
is the energy of the Rydberg
electron, we finally get that it arises when E
k
>1
ı
2n
2
. Consequently, for a given
initial kinetic energy of
E
k
the suppression of the AI reaction will occur when the
principal quantum numbers
1
p
2E
k
n>n
D
:
(1.40)
From the law of conservation of the total energy conservation expressed in the
form of
E
k
C
E
C
D
e
.X
C
Y/
I
XY
D
"
e
C
E
v
N
("
e
and E
v
N
are the released electron energy and the energy of the XY
C
ion
rovibrational excitation), it follows that because of the strong nonadiabatic coupling
of electronic and nuclear motions in the intermediate complex XY
**
(which is
responsible for the inhomogeneity of the ionization continuum spectrum), the
formation of the ion XY
C
can be accompanied by vibrational and rotational
excitation with the E
v
N
E
energy. It is also expected, by Eqs.
1.15
,
1.21
,and
1.22
, for the electron energy "
! the final rotational quantum number
N
can be
large enough (N
1) that it leads to a strong twisting of the XY
C
ion. It takes place
as the result of the ionization continuum inhomogeneity through the nonadiabatic
coupling between auto-decaying (ionization and predissociative) states of the closed
channels. The latter can be a kind of manifestation of the AI dynamics, because
statistically it is more advantageous (exothermic process).
This point means that in the general scheme must be included a large number
of the vibrational
v
and the rotational
N
quantum ones. Therefore, the resulting
spectrum of highly excited quasi-molecular states will contain a large number of
interacting Rydberg series, and as a consequence, the dependence of the levels of
the principal quantum numbers
n
for each series will be significantly irregular.
The procedure for determining the quantum defect levels and their distribution
on the relevant series in the general case is not unique. Moreover, starting with
certain values, the classification levels of highly excited states of the system
generally becomes impossible, i.e., comes to the stochastic regime (Casati et al.
1985
; Lombardi et al.
1988
; Gutzwiller
1990
; Lombardi and Seligman
1993
).
A special technique is required because the solution of such a multichannel problem
is extremely difficult. Expansion coefficients of the total wave function for this
series for large values of
n
and
N
behave almost unpredictably, as is typical for
multichannel-quantum systems (Golubkov and Ivanov
2001
). It is also known that in
regions of the strong nonadiabatic coupling (when the levels belonging to different
series of energy are close) there is repulsion of the levels of the degenerate states
by the interaction between them. Giving all these circumstances, it is advisable,
in general, to refuse a classification of the interacting highly excited states and
go to a random walk over the Rydberg levels in the transitions between them.
