Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

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Journal of Quantitative Spectroscopy &

Radiative Transfer
journal homepage: www.elsevier.com/locate/jqsrt

Tables of radiative transition probabilities for the main

diatomic molecular systems of OH, CH, CH , CO and CO
occurring in COH2 syngas-type plasma
T. Billoux, Y. Cressault, A. Gleizes n
Universit de Toulouse, CNRS ; UPS-INP, LAPLACE, 118 route de Narbonne, Toulouse cedex 9, France

a r t i c l e in f o

abstract

Article history:
Received 31 January 2013
Received in revised form
27 August 2013
Accepted 5 September 2013
Available online 18 September 2013

This paper focuses on the calculation of the radiative transition probabilities for the main
diatomic molecules contributing to the discrete radiation of COH2 syngas plasma. We
propose extensive tables of rovibrational transition probabilities for the main electronic
systems of OH, CH, CH , CO and CO . The rotational dependence of the nuclear wavefunctions was included in our calculations to take into account the coupling between the
rotational and vibrational motions. References are also given to data for O2, C2 and H2
molecules already published in the literature. The calculations were performed using the
RydbergKleinRees (RKR) inversion procedure for the reconstruction of the potentialenergy curves and an improved Numerov-type method was used to obtain the rovibrational wave-functions by solving the radial Schrdinger equation. We rigorously selected
the most up-to-date equilibrium spectroscopic constants for the RKR procedure and the
most accurate electronic transition moment functions (ETMF) available in the literature.
The results obtained with this procedure were systematically validated by comparison
with available experimental observations.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
COH2 plasma
Diatomic molecules
Transition probabilities
Vibrationalrotational coupling

1. Introduction
Characterising the radiative contribution of molecular
species in a plasma is a fundamental task in a large variety
of fields. Molecular radiation occurs in plasma devices
(syngas or biofuel reactor, reaction chemistry), spectroscopic diagnostics, astrophysics problems (atmospheric
entries, stellar radiation) and meteorology composition
analysis. This task requires an extensive and accurate
database of transition probabilities to describe the spectra.
In some temperature and pressure conditions, for an
exhaustive description of the radiative phenomena occurring in the plasma, knowledge of the atomic contribution
could be sufficient. For example in the centre part of high

Corresponding author. Tel.: 33 561 558 433.

E-mail address: alain.gleizes@laplace.univ-tlse.fr (A. Gleizes).

0022-4073/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jqsrt.2013.09.005

intensity arcs, the molecular contribution can often be

ignored. However, for lower temperature regions in arc
plasmas, combustion devices, atmospheric entries and in
the more general case of the peripheral absorbing regions
of plasma devices, the molecular contribution cannot be
neglected.
Some molecular radiative databases were built to
operate at atmospheric pressure and low temperatures.
Critical limitations emerge for high pressure conditions
due to temperature shift of the molecular dissociation
which increases the predominance of molecules toward
higher temperatures. Then at the higher temperatures,
some important electronic systems could be omitted and
in the same way the radiative database could be restricted
to low vibrational levels.
The molecular database RADEN [1] covers a lot of diatomic
electronic systems but the transition probability tables are
not public. Nevertheless, some useful recommendations are

T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

given for the selection of the most accurate transition

moments to use [2]. The AX, BX and CX electronic
systems of CH and AX system of OH were accurately treated
in LIFBASE [3] but some electronic systems are missing for
model applications. Thus we decided to compute all the
systems of CH and CH .
We present an extensive and exhaustive molecular
radiative database which takes into account all the diatomic contributions encountered in COH2 plasma. To
ensure that it remains valid for the full range of working
conditions, our transition probability tables were extended
to the high vibrational and rotational levels to cover a large
range of temperatures (300K15kK), preventing some
molecular systems from becoming preponderant as a
result of the shift of the temperature dependant dissociation rate with pressure (1100 bars). We report extensive
tables of rovibrational transition probabilities for the main
molecular systems occurring in COH2 plasma. The main
electronic systems of the OH, CH, CH , CO and CO
molecules were investigated.
We calculated the transition probabilities for the AX
violet and the XX Meinel electronic systems of OH, for the
XX, AX, BX and CX electronic systems of CH, for the
AX system of CH , for the XX infrared and the AX
fourth positive systems of CO and for the AX Comet-Tail,
the BX first negative and the BA BaldetJohnson systems of CO . The electronic systems of O2, C2 and H2 were
not dealt within this paper since these electronic systems
have either already been studied in detail elsewhere or did
not appear predominant in COH2 plasma radiation. All
references for transition probability tables in the literature
are given in this paper.
The present paper is organised in five parts. In Section 2
we briefly describe the context of the work and how the
transition probability tables can be used. In Section 3, the
RydbergKleinRees (RKR) procedure for the calculation of
the molecular potential curves is briefly described. In
Section 4, we develop a Numerov-type procedure used
for the calculation of the rovibrational wave-functions by
solving the radial Schrdinger equation. In Section 5, the
transition probabilities and the corresponding radiative
lifetimes obtained with this procedure are systematically
compared with available experimental and theoretical
results. Finally extensive transition probability tables for
each electronic system of interest are given under electronic form in the online version.
2. Background
The integrated intensity due to the spontaneous emission of a single molecular or atomic line is given by the
relation
A ul W m  3 sr  1

nu Aul hcsul
4

Using expression (1), three parameters are required to

characterise each line transition:
 The emitting population number density nu.
 The line position sul related to the energy difference
between the two ideal unperturbed states.

435

 The Einstein spontaneous emission coefficient Aul corresponding to the transition between the upper and the
lower rotational states involved.
The Aul expression depends on the electronic, vibrational, rotational, fine and hyperfine structure of the
molecule [4]. We restricted this work to the calculation
of the spin-allowed electronic dipolar transitions. By
investigating the equilibrium composition of COH2
plasma covering the whole range of temperature, pressure
and element ratios considered in this work, the main
diatomic molecules selected for calculations were CO,
OH, CH, O2, C2, H2, CO and CH . Some high energy
electronic states are not significantly populated for the
whole range of temperature and pressure conditions
retained in this work.
We recommend the tables of Abgrall et al. [5] and of
the Observatoire de Paris [6] for the H2 molecule as they
stand since these authors accurately treated the rotational
dependence of the transition probabilities. Some higher
electronic systems were treated by Fantz and Wnderlich
[7] using the TraDiMo computer program. The latter
authors dealt with a lot of high energy electronic systems
of H2 including some double potential minima electronic
systems, but rotationvibration coupling was not included.
The electronic systems of C2 and O2 are not predominant in the radiative properties of COH2 plasma and were
not investigated in this paper since an accurate description
of their radiative properties was proposed by Babou et al.
[8] for C2 and by Chauveau [9] for O2. These transition
probability tables can be widely used to make spectral
simulations for these molecules. We did not find data
concerning the potential barrier appearing for the third
positive system of CO. For this reason, we decided to use
the tables proposed by Babou et al. [8] as they stand.
The triatomic radiative contribution of CO2, H2O and
CH4 could predominate at low temperatures, but this topic
will not be developed here since some accurate and
extensive databases of line positions and transition probabilities exist like CDSD-4000 [10] for CO2, HITEMP [11] for
H2O and HITRAN [12] for CH4.
3. Description of the procedure for the calculation of the
rovibrational transition probabilities
We ignored the spin-splitting and lambda-doubling of
the rotational levels in the calculation of the rovibrational
wave-functions since, for the molecules involved in this
paper, the rovibrational transition probabilities depend
mainly on the coupling between vibrational and pure
rotational motion. The energy separation of the rotational
levels due to the spin-splitting and lambda-doubling
effects is smaller than the energy separation for two
adjacent pure rotational levels N. Thus the molecular levels
will be simply labelled (assuming Hund's coupling cases b
or intermediate a/b) by the electronic n, vibrational v, and
pure rotational N quantum numbers. We calculated the
transition probabilities for the P, Q and R rotational
branches (N 0, 71) for all electronic systems, and for
the O and S branches (N 72) for molecules assuming
allowed transitions with N 72.

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T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

Taking into account the rotational dependence of the

transition probabilities, the spontaneous emission Einstein
coefficient Aul for a molecular transition is then usually
expressed by the product of the rovibrational transition
probability pvv
NN and the HnlLondon factor as follows:
Aul

64 4 s3ul pvv
NN SJJ
3h
2J 1

sul is the line position in cm  1, pvv

NN corresponds to the
rovibrational transition probability (in a.u.) and SJJ refers
to the HnlLondon factors which describe the relative
intensity between each rotational branch for a given total
rotational level J. These coefficients have to be normalised
with the convention proposed by Whiting [13] (as a
consequence it induces the normalisation convention for
pvv
NN ):
J SJJ 2  0; 2S 12J 1

The tables of HnlLondon coefficients for each kind of

electronic transition (S2S) were summarised by
Kovcs [14]. The HnlLondon factors closely depend on
the type of Hund's coupling considered (a, b, intermediate
a/b) and on the resolved degeneracies of the fine and
hyperfine structures of the rotational levels. In this paper
we assumed that all electronic states belong to the b or
intermediate a/b Hund's coupling cases. The labelling for
the rotational branches corresponding to the same N are
summarised in Table 1. The rovibrational transition probability pvv
NN could then be safely multiplied with the
corresponding HnlLondon factors to perform spectrum
calculations.
The analytical expression for the transition probability
pvv
NN obeys to the relation
 Z
pvv
NN

1
0

v;N r Re r v;N r dr

2
4

Re(r) is the electronic transition moment function (ETMF),

v;N r and v;N r are the nuclear rovibrational wavefunctions for the upper and lower levels respectively and r
is the internuclear distance. For more theoretical details
we invite the reader to refer to the extensive description
proposed by Hertzberg [4] and Hougen [15].
A fundamental step of our work was the calculation
of the rovibrational wave-functions occurring in (4) by

Table 1
Rotational branch labelling for b and a/b Hund's coupling case.
N N
N
N  2
N  1
N 0
N 1
N 2

 1

 1

 2

P11,
P22,PQ12

Q
R

5
with Ev,N corresponding to the rovibrational energy eigenvalues, the reduced mass, U0(r) is the potential energycurve which is added to the centrifugal term, is the
reduced Planck's constant and N is the pure rotational
quantum number.
The preliminary step of this work consisted in the
calculation of the potential-energy curve U0(r) which
comes into play in Eq. (5). Then the radial Schrdinger
equation was solved to calculate the rovibrational wavefunctions. Finally, using the most up-to-date electronic
transition dipole moment function Re(r) given in the
literature, we calculated the rovibrational transition probabilities of interest pvv
NN for all the vibrational bands. This
procedure was systematically used for all the electronic
systems summarised in Table 2.

3.1. Reconstruction of the potential-energy curves: the RKR

inversion method
We used the well-known RydbergKleinRees inversion procedure for the reconstruction of the rotationless
potential curves. The original RKR inversion procedure,
bearing the name of its main contributors Rydberg [26],
Klein [27] and Rees [28] is based upon the WKB (Wentzel
KramersBrillouin) semi-classical approximation which is
implicitly included in the BornOppenheimer approximation as well as the adiabatic assumption. The procedure
consists in finding the vibrational turning points rinner(v)
and router(v) of the internuclear rotationless potential U0(r).
Table 2
Electronic molecular systems and electronic dipole moment references.
Molecule Electronic
system

Upper-lower
states

ETMF selected vmax : vmax

Re(r)

CO

Infrared

X1 X1

[16]

(49:40)

Fourth
positive

A1 X1

[17]

(22:35)

Comet-Tail

A2 X2

[18]

(30:26)

First
negative
Baldet
Johnson

B2 X2

[19]

(30:35)

B2 A2

[19]

(30:26)

CO

OH

 2, 2 2 or
2
 2
O

R11,
R22,RQ21

solving the nuclear radial Schrdinger equation given by

"
!#
2
d v;N r 2
NN 12

E

U
r

v;N r 0
v;N
0
dr 2
2r 2
2

Q12
P11,P22,PQ12

CH

Q11,Q22,QP21,QR12
R11,R22,RQ21
S

R21

CH

Meinel

X2 X2

[20]

(13:12)

Violet

A2 X2

[21]

(9:13)

Infrared

X2 X2

[22]

(12:11)

A2 X2

[23]

(7:12)

B2  X2

[24]

(1:12)

C2 X2

[24]

(2:12)

A1 X1

[25]

(10:17)

T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

Table 3
Molecular spectroscopic constants and vibrational limit of experimental
data for each electronic state.
Molecule
CO

CO

OH

CH

CH

Electronic state Ref. for Dunham Yij

Ref. for De vMAX

exp

X1

[29]

[30]

41

A1

[31]

[30]

23

X2

[32]

[19]

A2

[32]

[19]

B2

[33]

[19]

X2

[34]

[34]

13

A2

[34]

[34]

X2

[35]

[36]

A2

[35]

[36]

B2

[37]

[36]

C2

[38]

[36]

X1

[39] (curve)

A1

[39] (curve)

the calculation of the vibrational wave-functions. Note that

it is not a crucial point since the main information on the
oscillatory properties of the wave-functions comes from
the central part of the potential curve but it could
significantly affect the results obtained for the higher
vibrational levels. As proposed by Chauveau [40], the
attractive wing of the potential was extrapolated using a
HulburtHirshfelder function, and we used a parametric
power potential for the repulsive wing according to the
following expressions:
U rep r

a
rb

10

 r  r e 2
U HH
3 r  r e 3
att r De 1  e

e  2r  re 1 r  r e 

The vibrational G(v) and rotational B(v) energy terms

were calculated in the Dunham polynomial expansion
formalism as follows:






1 i
1
1 2
 e xe v
Gv i 1 Y i0 v
e v

2
2
2
6




1 i
1

Be e v
Bv i 0 Y i1 v
2
2

437

where Yij are the Dunham polynomial coefficients which

are intimately correlated to the equilibrium spectroscopic
constants. The references for the spectroscopic constants
used for the RKR procedure are summarised in Table 3 for
each electronic state.
The two auxiliary functions introduced by Klein [27] to
calculate the turning points were used as follows:
s Z
v
h
dv
1
p r outer v  r inner v
f v
8 2 c v0 Gv Gv 2

11

De is the dissociation energy of the electronic state, re the

equilibrium internuclear distance, and a, b, , and are
the adjustable parameters obtained by fitting the last
points of each RKR potential wing.
The potential-energy curves were reconstructed with
an iteration step of v 0.01 until v 1, and then with
v 0.1 until the experimental limit vMAX
exp of Table 3. The
integrals of f(v) and g(v) diverge at the neighbourhood of
the upper limit, where v approaches v. The convergent
part of the integral was performed by a Simpson procedure
with a resolution of 10  6 and the divergent part was
calculated using a 96-point Gauss-type quadrature
approximation.
The rotationless potential curves U0(r) obtained by this
procedure for all the electronic states of interest in this
paper are represented in Figs. 1, 4, 7, 10 and 12. These
potentials were now injected in the nuclear radial Schrdinger Eq. (5) to calculate the energy eigenvalues and the
rovibrational wave functions required for the calculation of
the rovibrational transition probabilities.
3.2. Procedure for the calculation of the rovibrational wave
functions
Using the RKR potential curves U0(r) previously
obtained, we now have to solve the nuclear radial Schrdinger Eq. (5). In this work we used the log derivative

8
r Z


8 2 c v Bv dv
1
1
1
p

gv
h
Gv  Gv 2 r inner v r outer v
v0
9
where v0 is the value of the vibrational level for which the
Dunham polynomial became nil.
This method allows a step by step reconstruction of the
rotationless potential curves U0(r) until the corresponding
experimental vibrational limit of the spectroscopic constants used. Above the vibrational limit of the observed
experimental lines, the RKR method is not valid because
Dunham polynomial fit becomes meaningless. It is then
necessary to extrapolate the attractive and repulsive wings
of the RKR potential curve to ensure the convergence of

Fig. 1. Calculated potential curves for the X1 and A1 electronic

states of CO.

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T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

Fig. 2. Comparison of the radiative lifetimes calculated in the present

work for the A1 electronic states of CO with the references (a) [8], (b)
[49], (c) [17], (d) [47] and (e) [48].

Fig. 5. Comparison of the radiative lifetimes calculated in the present

work for the A2 electronic states of CO with the references (a) [8], (b)
[19], (c) [18], (d) [51] and (e) [52].

Fig. 3. Comparison of the vibrational Einstein coefficients of the X1

electronic states of CO calculated in the present work with the references
(a) [50], (b) [16], (c) [8] and (d) [9].
Fig. 6. Comparison of the radiative lifetimes calculated in the present
work for the B2 electronic states of CO with references (a) [8], (b)
[19], (c) [18], (d) [53] and (e) [54].

Fig. 4. Calculated potential curves for the X2 , A2 and B2 electronic

states of CO .

method proposed by Johnson [41] based on the previous

works of Cooley [42] and Blatt [43] to resolve the eigenvalue problem. The particular solutions of (5) were

Fig. 7. Calculated potential curves for the X2 and A2 electronic

states of OH.

T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

Fig. 8. Comparison of the radiative lifetimes calculated in the present

work for the X2 electronic states of OH with the references (a) [56], (b)
[57] and (c) [58].

Fig. 9. Comparison of the radiative lifetimes calculated in the present

work for the A2 electronic states of OH with the references (a) [21], (b)
[34], (c) [60], (d) [61] and (e) [62].

Fig. 10. Calculated potential curves for the X2 ; A2 ; B2  ; and C2

electronic states of CH.

439

Fig. 11. Comparison of the radiative lifetimes calculated in the present

work for the A2 electronic states of CH with the references (a) [64], (b)
[65], (c) [23], (d) [66], (e) [67] and (f) [68].

Fig. 12. Calculated potential curves for the X1 and A1 electronic

states of CH .

calculated using the improved Numerov-type iteration

proposed by Simos [44] which upgraded the original
Numerov procedure by extending the interval of periodicity. Thus, using a small internuclear distance step of
10  20 m for the integration, the accuracy of this method
can be considered as suitable.
The vibrational eigenvalues obtained were then compared with the experimental energies calculated with the
Dunham polynomial expansion. Our results are in very
good agreement with the experimental vibrational energies. In the experimental range of vibrational and rotational levels the relative deviation of the calculated
rovibrational energy eigenvalues compared with the
experimental ones never exceeds 0.2% (encountered for
the higher vibrational levels), and tends to be 0% for the
lower vibrational levels. It validates the accuracy of the
calculated rovibrational wave-functions and thus of the
whole calculation procedure used in this paper. We calculated the complete set of rovibrational wave functions
nv;N r for all electronic states n involved in the electronic
systems of interest.

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T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

3.3. Calculation of the transition probabilities

Larsson [45] proposed a formalism for the expression of
the rovibrational Einstein coefficient AvN
vN and for the
radiative lifetime n
v of an electronic state (svv has to be
expressed in cm  1 and pvv
NN in atomic units):


2  0; vv
6
AnvN
sul 3
12
pNN
nvN 2:026:10
2 0;
n
v;N

1
n;v;N AnvN
nvN

13

The accuracy of the transition probabilities obtained in

the end closely depends on the accuracy of the wavefunctions, but even more on the accuracy of the ETMF used
in the calculation. Large discrepancies exist between the
various ETMF published in the literature and particular
attention has to be paid to select the most reliable. We
expected the selected ETMF to accurately reproduce the
various experimental observations and radiative lifetimes.
Moreover, we also expect these ETMF to be defined over a
large range of internuclear distances to ensure the description of the highest vibrational wave-functions. The ETMF
must absolutely cover the entire internuclear region where
the overlapping of the upper and lower wave-functions is
not nil to make an exhaustive description of the transition
probabilities.
The ab initio calculations of the ETMF are usually
defined for a large range or internuclear distance but have
the disadvantage of being closely dependent on the
electronic orbital basis set used and large discrepancies
occur between the various methods used. The experimental ETMF obtained by inversion of the observed line
intensity are quite accurate and, naturally, provide an
accurate reproduction of the experimental radiative lifetimes of reference but are restricted to the internuclear
range where the molecular lines are observed. So this
direct experimental inversion method by the r-centroid
approximation cannot apply to the higher vibrational
levels.
For the elaboration of an extensive transition probability database which includes the high vibrational levels and
which allows calculations at temperatures up to 15 kK, we
systematically preferred ab initio ETMF rather than the
experimental ones for our calculations. We finally ensured
that radiative lifetimes obtained for each electronic state
using ab initio ETMF were in satisfying agreement with
experimental ones. We summarised in Table 2 the selected
ETMF used to compute the transition probability tables
published in Appendix A.
4. Validation of the transition probabilities for the
electronic systems
The set of equilibrium spectroscopic constants used in
the KleinDunham polynomial expansion formalism for
the computation of the energy potentials will not be
detailed more here for each electronic state. We have
pragmatically used the more recent set of equilibrium
spectroscopic constants based on the largest number of

vibrational levels observed. All the references for the

computation of the RKR procedure are given in Table 3.
A systematic validation of the rovibrational transition
probabilities obtained by the procedure described in the
previous sections is difficult since the experimentally
observed rotational lines depend on many parameters like
the populations of the rotational levels, the line positions
and the line shape. For this reason we have pragmatically
chosen to validate our results by comparing the vibrational
lifetimes obtained with our calculations with the experimental ones. So ignoring the rotational dependence of the
transition probabilities in a vibrational band, according to
Larsson [45], we obtain the vibrational Einstein coefficients Avv and the corresponding vibrational radiative
lifetime n
v; :


2 0; vv
6
An;v
sul 3
14
p0;0
n;v 2:026:10
2  0;
n
v

1
n;v An;v
n;v

15

For all the electronic systems summarised in Table 2, we

will briefly justify our choice for ETMF by a critical analysis
among those reported in the literature. Then, the radiative
lifetimes and the vibrational Einstein coefficients obtained
using the selected ETMF were systematically compared
with the experimental and theoretical results already
published in the literature. Validations for the highest
vibrational levels were difficult since the experimental
observations are restricted to the vibrational levels where
rotational lines were observed. We systematically used the
ab initio ETMF which present the best agreement with
experimental radiative lifetimes and are defined in the
larger range of internuclear distances. Whenever possible,
we used unperturbed ETMF which are usable for a large
field of applications since possible corrections could be
added during the spectrum calculation procedure to take
into account the perturbations using predissociation rates
and perturbed spectroscopic constants. The tables of
vibrational transition probabilities proposed in this paper
do not take into account the perturbations occurring on
some individual vibrational levels and the predissociation
and cascade effects possibly affecting the population of
some vibrational levels. It explains the discrepancies
observed between our results and some experimental
ones for vibrational levels of perturbed electronic states.
4.1. CO electronic systems
The fourth positive system A1 X1 of CO greatly
contributes to the discrete radiation of the COH2 plasma
in the VUV region and has been thoroughly investigated in
the literature. We retained this electronic system for the
validation of the whole procedure used in this paper. Using
various ETMF, we compared the vibrational Einstein coefficients and the calculated radiative lifetimes obtained by
our method with those published in the literature. The
best agreement with the experimental radiative lifetimes
was obtained with the ab initio ETMF of Kirby and Cooper
[17] as shown in Fig. 2. Kirby and Cooper explained the
increasing behaviour of their theoretical radiative lifetimes

T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

versus the decreasing behaviour of the experimental ones

by the strong perturbations and predissociation effects
caused by the nearby states. Moreover, some pressure and
cascade phenomena strongly affect the exited electronic
states of CO and could make experimental measurements
difficult. These authors proposed a critical review of the
previous ETMF published to justify the accuracy of their
results. Finally, the ETMF of Kirby and Copper was confirmed by the later experimental works of Chan et al. [46].
Compared to the transition probabilities published by
Babou et al. [8], maximal discrepancies never exceeded
3% for the individual Avv (maximal deviation encountered
for the highest vibrational bands), and less than 0.3% for
the radiative lifetimes. This very weak difference validates
our integral procedure in comparison with the matrix
method for the resolution of the Schrdinger equation
since we have used the same ETMF. As shown in Fig. 2 we
obtained a very good agreement compared with the
radiative lifetimes of Kirby and Cooper [26]. Some discrepancies appear versus the experimental lifetimes of
Field et al. [47] and Imhof and Read [48] but our results
are still in reasonable agreement with these experimental
results. The differences are largely explained by the perturbations affecting the A1 state for the experimental
measurements. Our results differ significantly from those
of Lino Da Silva and Dudeck [49]. As pointed out by Babou
et al. [8], this discrepancy is probably explained by the
large difference between the FranckCondon factors of Ref.
[49] and ours.
For the infrared X1 X1 system of CO, we
retained the ab initio ETMF of Langhoff and Bauschlicher
[16] rather than that of Okada et al. [50] since it gives a
better reproduction of the transition probabilities of the
well-established HITRAN database [12] for the fundamental. Nevertheless both give a good reproduction of the
experimental observations for the first and second overtones. A critical review of the earlier empirical and ab initio
ETMFs was proposed in Ref. [16]. We did not find experimental radiative lifetimes for the ground state of CO but
some Einstein coefficients for the fundamental, first and
second overtones were available to validate our results. As
shown in Fig. 3, a good agreement was observed compared
to the Einstein coefficients published in Refs. [16,50] and
otherwise with those of Babou et al. [8].
4.2. CO electronic systems
We selected the ETMF of Marian et al. [18] for the
Comet-Tail A2 X2 electronic system since it reproduces the experimental radiative lifetimes a bit better than
the ETMF of Okada and Iwata [19]. Nevertheless these two
ETMF's both gave very similar results for the higher levels.
As shown in Fig. 5, a remarkable agreement is observed
among all the theoretical and experimental radiative lifetimes for the A2 electronic state.
We preferred the ab initio ETMF of Okada and Iwata
[19] rather than those of Marian et al. [18] for the first
negative B2 X2 and BaldetJohnson B2 A2
electronic systems of CO . The more recent ETMF's of
Okada and Iwata have a similar dependence on the internuclear distance in comparison to those of Marian et al.

441

but reproduce the experimental radiative lifetimes a bit

better for the B2 state. Okada and Iwata. also published
the corresponding Einstein coefficients for the two individual transition systems involving B2 . Our results are in
good agreement with theirs for the first negative system
though our Einstein coefficients are around twice as high
as theirs for the BaldetJohnson system. Since our results
are close to those of Babou et al. [8] concerning the
FranckCondon factors, the discrepancies observed compared with Okada and Iwata [19] are possibly caused by
the use of a different degeneracy factor in relation (14). As
shown in Fig. 6, our results are in excellent agreement
with the various experimental lifetimes for the B2 state
of CO .
4.3. OH electronic systems
For the computation of the transition probabilities of
the Meinel system X2 X2 , we used the recent ETMF of
Van der Loo and Groenenboom [55] rather than those of
Langhoff and Bauschlicher [20] as it provides a good
reproduction of the experimental radiative lifetime
observed for the first vibrational level as shown in Fig. 8.
For the 1st positive system A2 X2 of OH, the ab
initio ETMF of Bauschlicher and Langhoff [21] was used. It
was validated by the experimental observations of Steffens
et al. [59] and then by Luque and Crosley [34]. As shown in
Fig. 9, the radiative lifetimes obtained using this ETMF are
in excellent agreement with the experimental results.
4.4. CH electronic systems
For the infrared electronic system X2 X2 calculations, we used the theoretical ETMF of Lie and Hinze [22]
rather than the more recent one of Follmeg et al. [63]
because the latter was defined on too restrictive internuclear range. We did not find any experimental results to
validate our transition probabilities. Nevertheless, our
results are in perfect agreement with those calculated by
Lie and Hinze [64] using the theoretical transition matrix
elements.
We selected the more recent ETMF of Larsson and
Siegbahn [23] rather than that of Van Dishoeck [24] for
the first positive electronic system A2 X 2 . Using this
ETMF, we obtained an excellent agreement between our
radiative lifetimes for the A2 state compared with the
experimental ones as shown in Fig. 11.
Since the B2 state of CH presents a very smooth curve
and a potential barrier due to the high interaction caused
by the crossing interaction with the nearby states, we used
the more recent works of Kalemos et al. [36] obtained by
ab initio calculations but the height of this potential barrier
(811 cm  1, located at the distance of 1.85 10  10 m)
remains a subject of disagreement.
Then we constrained the fitting procedure to make sure
that the extrapolated attractive wing of the potential
passes through the barrier maximum and then smoothly
decreases until the dissociation limit. We used the ab initio
transition moment of Van Dishoeck [69] for second positive system B2  X2 . This ETMF was normalised to
the experimental lifetime value of 325 725 ns [67].

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T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

The potential-energy curve of the B2  state is strongly

perturbed by the nearby states and is not well-known,
thus it predissociates close to the level v 1 causing
high uncertainties. These perturbations explain the poor
agreement between the various results found in the
literature. Under these considerations, our calculations
for the Einstein coefficient ratios for the B2 state are in
excellent agreement with the experimental results of
Luque and Crosley [37] as shown in Table 4.
The C2 state presents a potential barrier too, due to
the crossing with the nearby state. As for the B2  , the
same procedure was used to describe this potential-energy
curve using the potential barrier height of 1630 cm-1
located at 1.746  10  10 m obtained by Kalemos et al.
[36]. The ab initio ETMF of Van Dishoek [69] was used
for the third positive system C2  X2 . The validation
of this system was made by comparing our results with the
intensity ratio of Jeffries et al. [71] as shown in Table 5. The
C2 is strongly predissociative as pointed by [67] and the
purely radiative lifetime has not been observed yet since
the natural lifetime for this state is too small. Nevertheless
our results accurately reproduce the emission intensity
ratio determined experimentally by Jeffries et al. [71]. An
excellent agreement was also found with the ab initio
radiative lifetimes obtained by Hinze et al. [64].

4.5. CH electronic system

The electronic systems of CH have not been extensively studied in the past. As noted by Carrington and
Ramsay [72], the A1 state is strongly perturbed by crossing interactions. The RKR procedure became useless for
this state since the vibrational energies cannot be fitted to
the polynomial form of Dunham. Even though the ground
state X1 could have been treated by the RKR procedure,
we chose to use the curves proposed by Helm et al. [39] as
the energy potential for the two states. These ab initio
Table 4
Comparisons of our calculated Einstein emission coefficient ratios to the
experimental results of Luque and Crosley [37] and Jeffries et al. Garland
and Crosley [70] for the B2  X2 transition of CH.
Ratio

This work

Luque et al.

Garland et al.

A01 =A00
A10 =A11
A12 =A11

0.028
0.87
0.164

0.031 70.005
0.85 70.08
0.165 70.02

0.067 0.02
0.5 7 0.2
0.3 7 0.1

Table 5
Comparisons of our calculated Einstein emission coefficient ratios to the
experimental results of Jeffries et al. [71] for the C2 X2 transition of
CH.
Ratio

This work

Jeffries et al.

A01 =A00
A02 =A01
A10 =A11
A12 =A11
A10 =A12
A13 =A12

0.0066
0.020
0.0123
0.0060
2.04
0.018

0.0053 7 0.001
0.0157 0.006
0.0095 7 0.005
0.00517 0.0014
2.0 7 1.1
o 0.05

Table 6
Calculated band oscillator strengths (x105) for the A1 X1 transition
of CH .
f(v,v)

This work

Larsson et al. [25]

(0,0)
(0,1)
(1,0)
(1,1)
(1,2)
(1,3)
(2,0)
(3,0)
(4,0)
(2,1)
(3,1)

545
105
325
89
101
28
138
54
21
242
216

545
108
331
88
100
29

Experimental
Weselak et al. [73]

342 7 6

172 9
757 8
407 5
246
211

potentials seem very accurate and were confirmed by the

measurements. We used the well accepted ETMF of Larsson and Siegbahn [25] for our calculations since it accurately reproduces the recent experimental observation.
Comparisons for the radiative lifetimes obtained were
quite difficult since we only found experimental values
for the first level. We decided to validate our results by
comparison of our absorption oscillator strength with
those published in the more recent works of the literature
as shown in Table 6. As expected, our results are in
excellent agreement with the theoretical results of Larsson
and Siegbahn, which tends to validate the potential curves
used. We also observed an excellent agreement with the
experimental oscillator strength of Larsson and Siegbahn
[25] but some small discrepancies appear compared with
Weselak et al. [73] when v increases. We think that
probably either the dipole moment of Larsson and Siegbahn is not correct at large internuclear distances or the
measurements of Weselak et al. are not accurate for the
higher vibrational levels. Anyway the observed discrepancies are not critical since the oscillator strengths for the
most intense bands are in remarkable agreement.
5. Conclusion
The aim of this paper was to propose extensive tables of
rovibrational transition probabilities for the main electronic systems contributing to the radiation process in COH2
plasma. The main electronic systems of CO, CO , OH, CH
and CH were investigated in this work. The calculations
were performed using the RKR procedure for the reconstruction of the internuclear potential curve of each
electronic state of interest. The most accurate spectroscopic constants were rigorously selected in the Dunham
polynomial formalism to obtain the expression of the
energy levels. Then the radial Schrdinger equation was
systematically solved with an improved Numerov-type
method to calculate the rovibrational wave-functions.
After a critical review of the ETMF published for each
electronic system, we finally calculated some extensive
tables of transition probabilities for the main molecular
transitions occurring in a COH2 plasma. The rotational
dependence of the rovibrational transition probabilities

T. Billoux et al. / Journal of Quantitative Spectroscopy & Radiative Transfer 133 (2014) 434444

were dealt with in our calculations. These arrays will then

be used for the computation of the emission and absorption coefficient spectra of the diatomic molecular lines
occurring in COH2 plasma.
Appendix A
The tables of rovibrational transition probabilities are
given under electronic form and can be found in the online
version of this article. The individual columns of the
supplementary data tables refer respectively to the upper
v and lower v vibrational levels, the upper N and lower
N pure rotational levels, and the transition probability
pvv
NN .
Appendix A. Supporting information
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/j.
jqsrt.2013.09.005.

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