410 cm
-1 . In addition, the mean collision velocity is smaller for heavier Rg
atoms. Both factors increase the mean collision time and favor statistical population of the CINAT channels for Rg = Ar − Xe.
Molecules possessing permanent electric quadrupole moments.
The long-range, * R
−4 , interaction between the I 2 E0
þ
g À D0
þ
u
or
I 2 f 0
þ
g À F0
þ
u
transition electric dipole moment and the permanent electric
quadrupole moments of M is strong in these cases (R is the distance between centers
of mass of the colliding partners). In pure iodine vapor, the I 2 0
þ
g $
I 2 ðXÞ
0
þ
u
are
dominant due to large I 2 (X) permanent electric quadrupole moment. The u $ g and
DX = 0 propensity rules are valid in these cases;
– Total, for all D state vibronic levels rate constants exhibit sharp maxima as
function of v E , and near-resonant CINATs have highest total rate constants.
Vibronic states nearest to the initial ones are mainly populated in the
near-resonant CINATs. The DJ = ± 1 and ‘DJ – large’ propensity rules are
valid in near-resonant and non-resonant CINATs, respectively;
– The E; v E
I 2 ðXÞ
D; v D and D; v E
I 2 ðXÞ
E; v D CINAT rate constants are similar;
– There are no distinct correlations between vibrational distributions (VDs) of a
state populated in CINATs and FCFs of initial and final vibronic levels, though
VDs ‘try’ to follow the trend in the FCFs with the initial states, but energy gap
law, P $ expðÀ
DE
j j
b Þ (b—is a variable parameter, usually, b = kT) ‘prevents’
this trend.
– Rate constants of non-resonant processes correspond to small impact parameters. In these cases, the CINATs are provided by orbiting of the I 2 (E or D) and
I 2 (X) colliding partners due to dispersion,—C 6 /R
6 , interaction. The orbiting
leads to population of several vibronic states in non-adiabatic transitions from
the initial to final I 2 states.
– For M = N 2 , CO 2 , the I 2 E0
þ
g À!
M D0
þ
u ; D
0 2 g ; b1 g ; d2 u ; c1 u
CINATs are also
occurred.
Molecules possessing permanent electric dipole moments.
– In this case, long-range interaction between the E-D transition electric dipole
and the permanent electric dipole of M, * R
−3 , is dominant, and the
I 2 0
þ
g $
M 0
þ
u
CINATs have to be the most probable. For these collision
partners, rate constants of quasi-resonant CINATs have to be huge, and VDs
have to be narrow, if energy mismatches are compensated by rotational transitions in a colliding partner.
Molecules possessing transition electric dipole moments.
5.5 Collision-Induced Nonadiabatic Transitions
185
-1 . In addition, the mean collision velocity is smaller for heavier Rg
atoms. Both factors increase the mean collision time and favor statistical population of the CINAT channels for Rg = Ar − Xe.
Molecules possessing permanent electric quadrupole moments.
The long-range, * R
−4 , interaction between the I 2 E0
þ
g À D0
þ
u
or
I 2 f 0
þ
g À F0
þ
u
transition electric dipole moment and the permanent electric
quadrupole moments of M is strong in these cases (R is the distance between centers
of mass of the colliding partners). In pure iodine vapor, the I 2 0
þ
g $
I 2 ðXÞ
0
þ
u
are
dominant due to large I 2 (X) permanent electric quadrupole moment. The u $ g and
DX = 0 propensity rules are valid in these cases;
– Total, for all D state vibronic levels rate constants exhibit sharp maxima as
function of v E , and near-resonant CINATs have highest total rate constants.
Vibronic states nearest to the initial ones are mainly populated in the
near-resonant CINATs. The DJ = ± 1 and ‘DJ – large’ propensity rules are
valid in near-resonant and non-resonant CINATs, respectively;
– The E; v E
I 2 ðXÞ
D; v D and D; v E
I 2 ðXÞ
E; v D CINAT rate constants are similar;
– There are no distinct correlations between vibrational distributions (VDs) of a
state populated in CINATs and FCFs of initial and final vibronic levels, though
VDs ‘try’ to follow the trend in the FCFs with the initial states, but energy gap
law, P $ expðÀ
DE
j j
b Þ (b—is a variable parameter, usually, b = kT) ‘prevents’
this trend.
– Rate constants of non-resonant processes correspond to small impact parameters. In these cases, the CINATs are provided by orbiting of the I 2 (E or D) and
I 2 (X) colliding partners due to dispersion,—C 6 /R
6 , interaction. The orbiting
leads to population of several vibronic states in non-adiabatic transitions from
the initial to final I 2 states.
– For M = N 2 , CO 2 , the I 2 E0
þ
g À!
M D0
þ
u ; D
0 2 g ; b1 g ; d2 u ; c1 u
CINATs are also
occurred.
Molecules possessing permanent electric dipole moments.
– In this case, long-range interaction between the E-D transition electric dipole
and the permanent electric dipole of M, * R
−3 , is dominant, and the
I 2 0
þ
g $
M 0
þ
u
CINATs have to be the most probable. For these collision
partners, rate constants of quasi-resonant CINATs have to be huge, and VDs
have to be narrow, if energy mismatches are compensated by rotational transitions in a colliding partner.
Molecules possessing transition electric dipole moments.
5.5 Collision-Induced Nonadiabatic Transitions
185