Chemical Physics 331 (2006) 18

www.elsevier.com/locate/chemphys

NN2 state to state vibrational-relaxation and dissociation rates

based on quasiclassical calculations
F. Esposito
a

a,*

, I. Armenise a, M. Capitelli

a,b

IMIP-CNR (Istituto di Metodologie Inorganiche e dei Plasmi, Consiglio Nazionale delle Ricerche), Via Amendola 122/D, 70126 Bari, Italy
b
Chemistry Department, Bari University, Via Orabona 4, 70126 Bari, Italy
Received 24 May 2006; accepted 27 September 2006
Available online 1 October 2006

Abstract
Interpolation formulas are presented to reproduce the rate coecients for vibrationaltranslational energy exchange and dissociation
for the N + N2 collision process. The original data have been obtained by quasiclassical method in a detailed way, including the eect of
molecular rotation. The tting procedure results are compared with original data and the related error is evaluated. Comparison with
global experimental dissociation results is also presented.
2006 Elsevier B.V. All rights reserved.
Keywords: Vibrational energy exchange; Rate coecients; Dissociation; Atom-molecule collisions; Nitrogen

1. Introduction
Nitrogen containing plasmas are of primary importance
in many elds of plasma technology including plasma
chemistry, plasma physics, hypersonic ows. Their characterization can be performed by using the methods of non
equilibrium plasma kinetics describing the electron and
heavy particle distribution functions which in general present strong deviations from the equilibrium distributions [1].
Particular attention has been devoted to the calculation of
non equilibrium vibrational distribution of N2, which
determines the behavior of the bulk properties of nitrogen
containing plasmas due to the coupling of this distribution
to the electron energy distribution function (eedf) and to
the chemical reactivity of the plasma. A lot of work has
been dedicated to this subject [2,3] also because of the
experimental diculty to detect the N2 non equilibrium
vibrational distributions, specially in the plateau and tail
regions. Strong attention has been devoted to the elementary processes entering in the state to state vibrational
*

Corresponding author. Fax: +39 080 592 9520.

E-mail address: fabrizio.esposito@ba.imip.cnr.it (F. Esposito).

0301-0104/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2006.09.035

kinetics. In particular VV (vibrationvibration) and VT

(vibrationtranslation) energy transfer processes largely
determine the shape of the vibrational distribution. Still
now the VT processes involving atomic nitrogen (VTa)
as well as the dissociation process induced by atoms from
each rovibrational state of N2, i.e. the processes
N2 v; j N ! N2 v0 ; j0 N

N2 v; j N ! 3N

represent a formidable problem in this kinetics. Some simplied methods have been developed in order to cope with
this problem, as reported in Ref. [4]. A good compromise
between reliability of results and computational resources
required is represented by the quasiclassical trajectory
method (QCT). The most known data obtained in this
way are those calculated by Lagana et al. [57] for the rst
process and by Esposito et al. [810] for both processes.
The data of Lagana et al. are not complete specially for
low lying and high lying vibrational levels and are to be
extrapolated for temperatures greater than 4000 K. On
the other hand the data recently improved by Esposito
et al. can be now considered a complete set of rates in
the whole vibrational range and in the temperature range

F. Esposito et al. / Chemical Physics 331 (2006) 18

5010,000 K. A comparison of the two sets of data for VT

rates, both obtained on a LEPS surface, shows a good
agreement into the common range of initial vibrational
states and temperature.
The aim of this paper is to present the rates for both
processes by means of interpolating formulas to be readily
implemented in kinetic and uid-dynamic codes, as well as
to improve our previous models [11,12]. The structure of
the paper is as follows. In Section 2 we briey describe
the method of calculation, in Sections 3,4 we present the
interpolation rates, in Section 4 we indirectly validate the
rates by comparing the whole dissociation rate of the process (2) with existing rates. In Section 5 we propose a set of
state to state dissociation rates induced by molecular
nitrogen.
2. Molecular dynamics calculations
We used quasiclassical method to calculate the cross sections for processes (1) and (2), considering the whole ladder
of rovibrational states supported by the diatomic potential
of the LEPS surface used [5,6] and obtained by WKB
approximation. We found 68 vibrational states, with a
maximum number of rotational states equal to 261 for
the vibrational quantum number v = 0. The software used
for these extensive calculations has been totally developed
by one of us [13], largely improved in these last years by
adding support for parallel and distributed computations,
and by applying an error check on trajectory calculation
which allows a very good overall performance, as explained
in Ref. [9].
Actually, some improvements have been applied to
original QCT data presented both in Ref. [9] and successively in Ref. [10]. We used a continuous range of translational energy from 103 to 10 eV (instead of 3 eV, as in

preceding works), a density of 96,000 trajectories per A

of impact parameter and per eV of kinetic energy in
the low energy range up to 0.5 eV, 24,000 up to 3 eV,
6000 up to 10 eV, with application of stratied sampling.
The extension of kinetic energy range from 3 to 10 eV is
of importance when calculating rate coecients, particularly for the dissociation process and for temperatures
higher than 4000 K. We have computed approximately
from 38 to 120 millions of trajectories for each vibrational state v considered, including all the rotational
states associated to v. Starting from v = 0, one vibrational state in ten has been considered, plus some new
other states of particular interest for a good interpolation: v = 1357656667. The cross sections are
obtained by discretizing the energy axis into 500 subintervals in order to have suciently good determinations
of thresholds (20 meV). Considering all the possible rovibrational states (about 10,000) as nal states is impossible from a practical point of view, because of the
unacceptable number of trajectories required but also
for the enormous kinetic code which should be set up
for using those data. Instead we obtained cross sections

from each initial rovibrational state towards each nal

vibrational state w, summing contributions from any nal
rotational state compatible with w. Then we calculated
rate coecients from a given vibrational state to each
possible nal vibrational state, averaging initial rotation
on a given rotational temperature. In all the presented
calculations, rotational temperature is equal to translational temperature.
3. Vibrationaltranslational rates
The rate coecients of the VTa process
N2 v N ! N2 w N;
calculated as discussed in the previous paragraph, have
been successfully interpolated by means of three dierent
formulas. The t has been performed in the vibrational
range of the reactant v = 166 on three variables: the translational-rotational temperature T, the vibrational state v of
the molecule before the collision and the vibrational quantum jump Dv. The rates corresponding to the last vibrational level v = 67 have also been interpolated, but
separately because these data present a quite anomalous
behaviour with respect to trends related to other vibrational levels.
The vibrational quantum jump Dv runs from 1 to 50;
remaining rates have been discarded because of the unacceptable statistical noise, due to the the extremely low typical value of them (much lower than 1030 cm3/s).
A temperature range T = 5010,000 K has been considered. This range holds for each formula and couple of (v,
Dv), hence it will not be mentioned anymore in the
following.
Various tting procedures have been tested for reproducing the dierent behaviours of the relevant rates,
including also Arrhenius terms in the formulas. In particular a study of the dependence of the logarithm of the rates
(expressed in cm3/s), on temperature and on initial vibrational level has been performed keeping Dv xed; in a second step also the Dv dependence has been interpolated. The
simplest way to put together all the relevant trends was to
use an additive model into the exponential argument, as
shown in the following expressions:
K VT v; T ; Dv exp a1 v; Dv a2 v; Dv=T a3 v; Dv=T 2
a4 v; Dv=T 3 a5 v; Dv lnT

3a

where
ai v; Dv zi0 Dv zi1 Dvv zi2 Dvv2 zi3 Dvv3
zi4 Dv lnv

3b

zij Dv bij cij Dv

3c

and
K VT v; T ; Dv expa1 v; Dv a2 v; Dv=T
a3 v; Dv=T 4 a4 v; Dv= lnT
where

4a

F. Esposito et al. / Chemical Physics 331 (2006) 18

ai v; Dv zi0 Dv zi1 Dvv zi2 Dvv2

zij Dv bij cij Dv

4b
4c

and nally
K VT T ; Dv expa1 Dv a2 Dv=T a3 Dv=T 2
a4 Dv=T 3 a5 Dv lnT

5a

where
ai Dv zi0 zi1 Dv zi2 Dv2 zi3 Dv3 zi4 lnDv

5b

zij bij

5c

Formula (3) has been used to interpolate the rates with

v = 166 and Dv = 130. Actually, due to the huge spread
in the magnitude of the rates, ve dierent sets of coecients bij and cij have been tabulated: one for Dv = 1 (second column on Tables 1 and 2), one for Dv = 25 (third
column), one for Dv = 610 (fourth column), one for
Dv = 1120 (fth column) and one for Dv = 2130 (sixth
column).
Formula (4) has been used to interpolate the rates in the
range v = 166 and Dv = 3150 (the corresponding bij and
cij are reported in the seventh column on Tables 1 and 2).
Finally, formula (5) has been used to interpolate the
rates with v = 67 and Dv = 150 (eighth column on Table
1). Note that formula (3a) and (5a) are equal, but not the
coecients in 3b, 3c and 5b, 5c.

Relevant interpolation coecients have been reported in

Tables 1, 2. A sample of rates, corresponding to some v (1,
10, 20, 30, 40, 50, 60, 67) and Dv (1, 10, 50) have been
reported versus T in Figs. 13.
The curves obtained by the interpolation formulas well
reproduce the QCT results, as can be appreciated by
inspection of the root mean square of the logarithm of
the t error:
errT ; v; Dv jlog10 RVT T ; v; Dv  log10 K VT T ; v; Dvj
!
X
2
errT ; v; Dv =n
6
RMS sqrt
T ;v;Dv

where n is the number of the terms in the sum, RVT(T, v,

Dv) are the QCT rates, KVT(T, v, Dv) the tted rates.
Actually dierent criteria have been adopted in neglecting some terms of the sum in Eq. (6). The rst criterion
regards the rate value: rates less than 1030 or, in another
case, 1015 cm3s1 have been neglected, this being justied
by the fact that too small rates do not aect the kinetics.
The second criterion regards the vibrational quantum
jump: the two dierent ranges of 1 6 Dv 6 30 and
31 6 Dv 6 50 have been selected. The third criterion concerns the translational temperature range that has been
xed to T = 5010,000 K, T = 30010,000 K, T = 500
10,000 K, T = 100010,000 K. The combinations of these
criterions have been reported in Table 3.

Table 1
bij parameters of Eqs. (3)(5) and (7)
i,j(+)

1,0
1,1
1,2
1,3
1,4
2,0
2,1
2,2
2,3
2,4
3,0
3,1
3,2
3,3
3,4
4,0
4,1
4,2
4,3
4,4
5,0
5,1
5,2
5,3
5,4

(3)(*)

(3)

(3)

(3)

(3)

(4)

(5)

(7)

v = 166
Dv = 1

v = 166
Dv = 25

v = 166
Dv = 610

v = 166
Dv = 1120

v = 166
Dv = 2130

v = 166
Dv = 3150

v = 67
Dv = 150

v = 067

31.892
0.49154
0.0033037
9.3628e5
3.5170
14136
426.97
11.295
0.088168
2445.9
7545.7
2282.0
76.152
0.85097
6103.3
4.5889e+5
1.5643e+5
4100.5
37.056
4.3938e+5
0.97969
0.056111
0.00033621
1.0524e5
0.38105

26.206
0.82551
0.0006123
9.8055e5
7.1611
2265.8
1615.8
31.141
0.21704
7257.2
2.3386e5
15716.
190.91
0.63382
1.5833e5
6.2281e6
3.1635e5
2992.2
2.8977
3.819e6
0.33331
0.097972
3.7562e6
1.106e5
0.8232

337.18
26.02
0.42491
0.0027002
228.37
28598.
286.7
2.3597
0.041736
10946.
2.0118e6
2.0423e5
3468.9
22.915
1.6538e6
3.8567e7
4.253e6
74326.
501.88
3.3094e7
35.987
2.9425
0.047671
0.00030079
26.054

514.48
18.119
0.20719
0.00096926
255.39
39503.
2329.
30.418
0.16017
25676.
5.5045e6
2.607e5
3365.9
18.14
3.1747e6
1.38e8
6.692e6
87986.
482.84
8.019e7
48.762
1.7422
0.01924
8.4801e5
25.111

1913.9
52.481
0.48857
0.0018799
900.59
51183.
1408.2
9.4815
0.0035057
25180.
2.8679e7
8.4972e5
8581.4
38.963
1.3952e7
1.3435e9
4.0984e7
4.1691e5
1873.6
6.6063e8
216.6
6.1832
0.058532
0.00022954
104.18

77.301
3.2693
0.028347

27.1378
1.4284
0.00917904
9.30145e5
7.35578
308.408
16.1689
2.44932
0.0401051
436.716
33753.1
19290
733.009
7.48912
24315.8
920867
578586
20604.9
205.009
919170
0.356391
0.192037
0.0019669
2.87492e6
1.0599

41.0228
0.395249
0.0281093
0.000272751

(+) The rst column reports the indices i,j of each coecient bij.
(*) Numbers in parentheses, in the top labels, refer to the equation number.

1449.
45.884
0.40501

2.4925e8
9.6916e6
90606.

669.53
21.
0.18086

113203
3502.12
31.0477
0.0602403
508188
16160.7
28.1276
2.41386
6.58482e+7
3.36049e+6
52891.5
257.497
2.0093
0.0608003
0.00336294
3.16653e5

F. Esposito et al. / Chemical Physics 331 (2006) 18

Table 2
cij parameters of Eqs. (3) and (4)
i,j (+)

1,0
1,1
1,2
1,3
1,4
2,0
2,1
2,2
2,3
2,4
3,0
3,1
3,2
3,3
3,4
4,0
4,1
4,2
4,3
4,4
5,0
5,1
5,2
5,3
5,4

(3)(*)

(3)

(3)

(3)

(4)

v = 166
Dv = 25

v = 166
Dv = 610

v = 166
Dv = 1120

v = 166
Dv = 2130

v = 166
Dv = 3150

5.6113
0.49123
0.00691
3.1854e5
4.3078
7957.6
805.55
13.449
0.087121
6528.7
1.5896e5
14496.
241.08
1.5321
1.5833e5
3.8861e6
3.4311e5
5689.7
36.334
2.9495e6
0.60787
0.060132
0.00082296
3.4935e6
0.5128

+35.251
+3.0704
0.04988
+0.00031795
26.734
+673.33
38.693
+1.1784
0.010247
91.913
+2.2119e5
+23162.
395.33
+2.6276
1.8497e5
4.0306e6
4.639e5
+8147.4
55.4
+3.5495e6
4.1939
0.3546
+0.0057291
3.6409e5
+3.1265

+35.807
+1.5012
0.018452
+9.4902e5
19.668
4267.8
208.6
+2.816
0.015949
+2471.9
+3.5566e5
+18018.
246.14
+1.4116
2.0944e5
7.9016e6
4.1084e5
+5732.9
33.548
+4.6909e6
3.9011
0.16334
+0.0020055
1.0272e5
+2.139

+111.8
+3.4639
0.0353
+0.00015356
55.237
7693.
261.78
+2.8496
0.013163
+3912.2
9.314e5
24726.
+222.47
0.87936
+4.3994e5
+4.9046e7
+1.4385e6
14021.
+59.747
2.3866e7
13.705
0.43641
+0.0045264
2.0079e5
+6.8319

2.9292
0.095619
0.000802

139.32
4.4195
0.034642

5.9289e6
2.3939e5
2354.8

16.603
0.53075
0.0042281

(+) The rst column reports the indices i,j of each coecient cij.
(*) Numbers in parentheses, in the top labels, refer to the equation numbers.

(v-w) = 1

(v-w) = 1

10-9
10 -12
10 -14

-18

10 -20
10

10-10

3 -1

10

k v+1->v (cm s )

3 -1

k v+1->v (cm s )

10 -16

v=1
v=10
v=20
v=30
v=1
v=10
v=20
v=30

-22

10 -24

v=40
v=50
v=60
v=67
v=40
v=50
v=60
v=67

10-11

10 -26
10 -28

10 -30
1000

10000

10-12
1000

10000

Fig. 1. VTa rate coecients by QCT calculations (points) and by interpolation formulas (curves) versus T at dierent initial vibrational level v and for a
vibrational quantum jump Dv = 1.

Depending on the adopted ranges, the RMS changes

signicantly: the maximum RMS is approximately a factor 4.6 with respect to the rate value (RMS = 0.6742, in
the range: T P 50 K, RVT P 1030, 31 6 Dv 6 50),
whereas the minimum RMS is 14% of the rate value

(RMS = 0.0573, in the range: T P 1000, RVT P 1015,

Dv 6 30).
For each RVT and Dv range (read: each column on Table
3), the RMS error decreases with the increasing of the minimum temperature included in its calculation: this means

F. Esposito et al. / Chemical Physics 331 (2006) 18

5
(v-w) = 10

(v-w) = 10
10-10
10-12
10-14

-18

10-20
10

10-11

3 -1

10

k v+1->v (cm s )

3 -1

k v+1->v (cm s )

10-16

v=40
v=50
v=60
v=67
v=40
v=50
v=60
v=67

v=10
v=20
v=30
v=10
v=20
v=30

-22

10-24

10-12

10-26
10-28

10-30
1000

10-13
1000

10000

10000

T
Fig. 2. Same as in 1 vibrational quantum jump Dv = 10.

(v-w) = 50

therefore large t errors occur just where original rate

results are aected by large incertitude.

3 -1

k v+1->v (cm s )

10-12

10

-13

10

-14

4. Dissociation rates
The dissociation rate coecients of the reaction (2) can
be satisfactorily interpolated as a function of the translational temperature and of the vibrational level v by the
formula

10-15

K d-sts T ; v expa1 v a2 v=T a3 v=T 2

v=50
v=60
v=67
v=50
v=60
v=67

10-16

10-17

a4 v=T 3 a5 v lnT
where

10-18
1000

7a

10000

ai v zi0 zi1 v zi2 v2 zi3 v3

7b

zij bij

7c

T
Fig. 3. Same as in 1 vibrational quantum jump Dv = 50.

that the rates in the higher temperature range have been

interpolated better than the others.
Generally speaking, inspecting Table 3 brings to the
conclusion that the higher the rate values, the lower the
t errors. This is a positive feature, because the rates are
aected by statistical errors too, with the same behaviour;

the coecients bij are reported on the last column of Table

1.
Note that formula (7b) diers from (3b) for the logarithm term.
In this interpolation, the temperature has been run in
the range T = 5010,000 K and the vibrational level of
the colliding molecule in the range v=067. We have
already published a t of dissociation rate coecients in
[14]. The comparison with that work, generally good,
shows that the older dissociation rate values are smaller

Table 3
Root mean square of the logarithm of the t error (cm3 s1), at dierent temperatures, vibrational quantum jumps and rate ranges

T P 50
T P 300
T P 500
T P 1000

RVT P 1030
Dv 6 30

RVT P 1015
Dv 6 30

RVT P 1030
31 6 Dv 6 50

RVT P 1015
31 6 Dv 6 50

0.3109
0.1650
0.1110
0.0651

0.1964
0.0751
0.0648
0.0573

0.6742
0.2178
0.1472
0.1038

0.3580
0.1634
0.1272
0.1038

F. Esposito et al. / Chemical Physics 331 (2006) 18

than those in the present work, particularly for temperatures higher than 7000 K (up to one order of magnitude
at 10,000 K), as a consequence of neglecting the 310 eV
range of kinetic energy in the QCT calculations (see Section
2).
Dissociation coecients are signicantly smoother than
the VT ones as a function of initial vibrational quantum
number, and the shape of dissociation trend as a function
of temperature is very simple. As a consequence, the search
for a suitable t of the dissociation rate coecients has
been actually easier than VT tting, with better results.
On Fig. 4 the dissociation rate coecients along with
molecular dynamic calculation results are shown for eight
dierent initial vibrational levels, showing a good
agreement.
The RMS error is considered also for dissociation rates:
errT ; v jlog10 Rd-sts v; T  log10 K d-sts v; T j
!
X
2
errT ; v =n
RMS sqrt

T ;v

n being the number of terms in the sum. The RMS values,

shown in Table 4, have been obtained neglecting dissociation rates less than 1030 cm3 s1 because they are too
small to aect the kinetics. The RMS error ranges between
20% and 30% of the rate value, the better result being relative to the 100010,000 K temperature range, whereas the
worse one to the whole range 5010,000 K.
Starting from the state-selected dissociation rates, a total
dissociation rate
X
K d T
N v=N K d-sts v; T
9
can be evaluated, where N is the molecular population density and N(v) is the population density of the v-th vibrational level. The vibrational distribution function has
been obtained running, at dierent temperatures, a zero-

10 -16

10 -22
10 -24

10

-28

10

-30

Present work (formula (9))

Park

Shatalov

1000
2000
3000
4000
5000
6000
7000
8000
9000
10,000

6.26E57
2.09E32
3.11E24
3.75E20
1.05E17
4.47E16
6.51E15
4.87E14
2.32E13
8.15E13

5.43E56
6.84E32
5.58E24
4.40E20
8.85E18
2.87E16
3.32E15
2.03E14
8.09E14
2.41E13

6.89E57
2.16E32
3.07E24
3.64E20
1.00E17
4.23E16
6.11E15
4.52E14
2.14E13
7.39E13

10 -12

10 -20

10

Table 5
A comparison of global dissociation rates (cm3 s1) for the process
N2 + N ! 3N at dierent temperatures

10 -10

10 -18

-26

0.1135
0.1033
0.0946
0.0850

dimensional kinetic code up to the vibrational equilibrium

[15].
These global rates can be compared with some of the
most used rates present in the literature (see e.g. [16]). In
particular we compare in Table 5 our results with the global rate reported by Shatalov [17] and by Park [18]. One
can appreciate an excellent agreement with the Shatalov
results in the whole temperature range. The comparison
with the Park results is more complicated; our rates infact
are lower than the Park ones up to 4000 K, then becoming
higher. Maximum deviation occurs at T = 10,000 K where

3 -1

3 -1

kdN2(v)+N->3N (cm s )

10 -14

v=0
v=10
v=20
v=30
v=0
v=10
v=20
v=30

RMS
T P 50
T P 300
T P 500
T P 1000

kdN2(v)+N->3N (cm s )

10 -12

Table 4
Root mean square of the logarithm of the t error of the dissociation rates
(cm3 s1) using dierent temperature ranges

10 -14
10 -16
10 -18
v=40
v=50
v=60
v=67
v=40
v=50
v=60
v=67

10 -20
10 -22
10 -24
10 -26
10 -28

a
1000

10000

10 -30
100

1000

10000

Fig. 4. The dissociation rate coecients by molecular dynamic calculations (points) and by interpolation formulas (curves) versus T at dierent initial
vibrational level v.

F. Esposito et al. / Chemical Physics 331 (2006) 18

calculated in the present work and available for the Park

and Shatalov data. Again we observe an excellent agreement with the Shatalov coecients while some dierences
are present with the Park coecients.
Before ending this section, we want to note that the
assessment of the accuracy of state to state rates through
the comparison of theoretical and experimental global
rates can be open to some criticism, not only for the oldness of experimental rates but also for the possibility of
non equilibrium vibrational distributions present under
actual experimental conditions. On the other hand the
use of state to state rates becomes necessary in order to
study dissociation-recombination processes under non
equilibrium conditions, when the Arrhenius type dissociation rates can not be applied (see e.g. [15]).

3 -1

kd N2+N -> 3N (cm s )

10-13

10-14

Appleton et al.
10-15

Byron
Hanson, Baganoff
Kewley, Hornung
present work (Table 5)

10-16
6000

7000

8000

9000

10000

5. Dissociation from moleculemolecule collisions

Fig. 5. Experimental (points) and present work (line) global dissociation
rate coecients versus T for the process N2 + N ! 3N.

A set of state to state dissociation rates of the process

N2 v N2 ! 2N N2

Table 6
Coecients of the Arrhenius-like dissociation rate Kd(T) (in cm3 s1)
Present work
Park
Shatalov

1.7004E07
0.049817
1.9761E07

0.095333
1.6
0.13

113700
113200
112982

our rate is a factor 3.4 higher than the Park rate. It is now
interesting to compare the present calculations with available experimental data [1922] reported in Fig. 5. It should
be noted that the experimental results are able to distinguish between the dissociation rates induced by molecules
and by atoms (see e.g. Ref. [20,21]). Inspection of Fig. 5
shows that our calculations lie in the between of all experimental data, being in very good agreement with results of
Hanson and Bagano, taking also into account their error
bars.
Table 6 reports the coecients of the dissociation rate
tted in the usual Arrhenius form:
K d T AT B exph=T

10

11

can be derived by the corresponding rates of process (2) by

2 N2
scaling these rates with the factor k N
=k dN2 N , i.e. the ratio
d
between the global dissociation rates induced by molecules
and by atoms. This procedure implicitly assumes that the
state to state rates behave like the global rates. The factor
2 N2
kN
=k dN2 N has been deduced by the rates of Park [18] and
d
Shatalov [17]. Park factor is equal to 0.23 while the Shatalov factor presents the following temperature dependence:
2 N2
2N
kN
T =k N
T 0:1694 5:5249E  5  T  5:2927E
d
d

 9  T 2 2:2742E  13  T 3
The state to state rates obtained according to this procedure have been inserted in a kinetic model to obtain the
global dissociation rates. They are named K Pd N2 N2 (T)
2 N2
and K SN
(T) when obtained using respectively Park or
d
Shatalov factor. Corresponding results have been reported
in Table 7. As expected the dierences closely follow those
described in Table 5. In the same table we have also reported the global rates obtained by Macheret and Adamovich [23] by using state to state dissociation rates of process
(11), obtained by a modied forced harmonic oscillator

Table 7
A comparison of global dissociation rates (cm3 s1) for the process N2 + N2 ! N2+2N at dierent temperatures
T

Present work
K Pd N2 N2 (T)

Present work
2 N2
K SN
(T)
d

Park

Shatalov

Adamovich

1000
2000
3000
4000
5000
6000
7000
8000
9000
10,000

1.44E57
4.80E33
7.16E25
8.64E21
2.41E18
1.03E16
1.50E15
1.12E14
5.35E14
1.88E13

1.37E57
5.45E33
9.13E25
1.20E20
3.59E18
1.61E16
2.44E15
1.89E14
9.38E14
3.42E13

1.27E56
1.59E32
1.30E24
1.03E20
2.06E18
6.71E17
7.75E16
4.73E15
1.89E14
5.61E14

1.52E57
5.66E33
9.03E25
1.16E20
3.42E18
1.52E16
2.29E15
1.76E14
8.64E14
3.09E13

1.33E18
5.10E17
7.69E16
5.14E15
2.16E14
7.18E14

F. Esposito et al. / Chemical Physics 331 (2006) 18

(FHO) model [23,24] in the impulsive approximation. The

agreement with these results can be considered satisfactory
especially taking into account the dierent methods used in
the calculations.
6. Conclusions
In this paper complete and detailed sets of vibration
translation and dissociation rate coecients are presented
for the collision process N + N2(v), as a function of rotational-translational temperature. The sets, obtained by
extensive quasiclassical calculations, have been tted in
order to use the data in detailed kinetic codes. The accuracy of the reported data has been assessed by comparing
derived global rates with existing calculated and experimental rates.
As a nal comment we suggest to use the present NN2
data for future applications in non equilibrium vibrational
kinetics. On the other hand QCT calculations involving
N2N2 collisions could be useful to increase the accuracy
of the present data.
Acknowledgements
The present paper has been partially supported by
MIUR under contracts Dinamica Molecolare di processi
elementari in condizioni di non equilibrio (MIUR PRIN
2005, Project No. 2005039049 005) and Dinamica Microscopica della Reattivita` Chimica (MIUR FIRB, Project
No. RBAU01H8FW 003).
The authors would like to thank Prof.Claudine Gorse
for very useful discussions and Dr. Giulia Capitta for collaboration in data tting.
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