Chemical Physics 491 (2017) 3341

Contents lists available at ScienceDirect

Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Theoretical electronic structure of the NaBe molecule

Wael Chmaisani a, Nayla El-Kork b, Mahmoud Korek a,
a
Faculty of Science, Beirut Arab University, P.O. Box 11-5020 Riad El Solh, Beirut 1107 2809, Lebanon
b
Khalifa University, P.O. Box 57, Abu Dahbi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: A theoretical study of the low-lying electronic states of NaBe molecule has been investigated via the
Received 21 January 2017 CASSCF/MRCI (single and double excitations with Davidson correcrtion) method using the correlation-
In final form 14 April 2017 consistent basis set pwCV5Z. Two sets of frozen core orbitals (FCOs) are adopted to estimate the correla-
Available online 27 April 2017
tion effect of the inner-shell electrons on the molecular properties. The spectroscopic constants are deter-
mined for the electronic bound states. The Einstein coefficients, the spontaneous radiative lifetime and
Keywords: the emission oscillator strength have been calculated for the lowest electronic transitions. The ro-vibra-
Ab initio calculation
tional parameters have been obtained for different electronic states by using the canonical functions
Electronic structure
Spectroscopic constants
approach. Twenty-two electronic states are studied theoretically here for the first time. Our evaluation
Potential energy curves of the potential energy curves leads to significantly off-diagonal Franck-Condon factors for the transitions
Dipole moments X2R+(2)2R+ and X2R+(1)2P which shows that the highly diagonal FCFs criterion for laser cooling is not
Franck-Condon factor verified for the NaBe molecule.
Rovibrational calculation 2017 Elsevier B.V. All rights reserved.

1. Introduction candidates [1521]. As well as, some experimental studies have

Currently, atomic and molecular physics fields testifie a rapid
and significant developments of the laser cooling of diatomic polar
molecules. The main experimental techniques using the ultracold
atoms to produce ultracold molecules are photoassociation [1]
and Feshbach resonance [2]. But they are limited to homonuclear
and heteronuclear alkali dimers [39] with singlet and triplet elec-
tronic states. The buffer-gas cooling is another experimental
method uses a cold inert buffer gaz to cool the molecules directly
through elastic collisions [1013]. Moreover, Shuman et al. [14]
introduce the first direct cooling of a polar molecule (SrF) by using
an optical cycling scheme with Doppler and Sisyphus cooling
forces. To achieve this process, the nominated molecules as laser
cooling candidates, such as alkali-alkaline earth species, must meet
certain theoretical criteria. i) The highly diagonal FCFs for a consid-
ered transition, which is practically limiting the number of lasers
required to keep the molecule in a closed-loop cycle. ii) The shorter
lifetimes of the excited electronic state for rapid laser cooling. iii)
There are no intervening electronic states to which the upper state
could radiate and terminate the cycling transition. iv) Deep knowl-
edge of the electronic structure and its ro-vibrational energy levels.
In the last decade the theoretical studies and the closed-loop
cooling cycle have been investigated for some ultracold molecules
Corresponding author.
E-mail addresses: Mahmoud.korek@bau.edu.lb, fkorek@yahoo.com (M. Korek).
been benefited from the laser cooling optical scheme [13,22,23],
but unfortunately there are no reports for the sodium-beryllium
molecule.
Recently there is a growing interest in the diatomic alkali-alka-
line earth compounds which are the most promising candidates for
laser cooling. Their 2R+ ground statepresents electric and magnetic
dipole moments which allow these molecules to control chemical
reactions at low ultracold temperatures [24]. Also, ultracold
molecules can be used to measure fundamental constants with
high-precision [25,26], as well as to control the preparation of
many-body entangled states [27]. In addition, due to the long-
range dipole-dipole interactions and the possible control precision
over rotation-vibration degrees of freedom at lowest temperatures,
such ultracold molecules can be used in quantum computation
[28] and in quantum simulation of lattice-spin models [29,30].
Several theoretical studies of the alkali-alkaline earth molecules
have been investigated. Pototschnig et al. [31] newly studied the
lowest doublet and quartet R+ electronic states of the alkali (Li,
Na, K, Rb)alkaline earth (Be, Mg, Ca, Sr) compounds via MCSCF
+ MRCI approach. Permanent electric dipole moment (PEDM) and
some spectroscopic constants (Re , xe , De ) along with the polariz-
ability for these states were also reported. Recently, the Be-alkali
compounds have received great attention and extensive theoretical
studies. Potential energy and dipole moment curves for the X2R+,
(2)2R+, (1)2P, (2)2P states of RbBe, CsBe [32], KBe [33] and also
of LiBe [21] are investigated by using MRCI method with large

http://dx.doi.org/10.1016/j.chemphys.2017.04.007
0301-0104/ 2017 Elsevier B.V. All rights reserved.
34 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341
and small-core approximations. The FCFs and the Einstein coeffi-
cients along with the optical scheme of (2)2R+ M X2R+ transition
have been obtained for LiBe molecule. Moreover, the spectroscopic
parameters Re , xe ; De for the ground state of the LiBe molecule and
its ion are calculated by using MP2(full)/6311+G basis sets [34].
Kotochigova et al. [35] presented PEC, DMC, spectroscopic para-
maters, and all vibrational energies of LiBe ground state by using
coupled-cluster method. LiBe molecule are also studied experi-
mentally by Fischer et al. [36]. The bond lengths, dissociation ener-
gies, and harmonic frequencies are calculated by Bauschlicher et al.
[37] for the lowest R+ electronic state for LiBe and NaBe com-
pounds and their negative ions by using CASSCF/MRCI technique.
But for NaBe species and its ion, different techniques have been
used to estimate the effect of 2s2p correlation in Na atom on the
Re and De constants. A theoretical study of hyperfine coupling con-
stants have been performed for LiBe, NaBe, and KBe by Bruna et al.
[38]. Consequently, some theoretical studies have been performed
for the low-lying excited states of the Be-alkali compounds except
for the sodium-beryllium molecule. Because of the lack in the the-
oretical and experimental studies of this molecule, and in order to
study the possibility of laser-cooling for the NaBe molecule, we
present in this work an extensive theoretical investigation of the
electronic structure of this molecule.
In the present work, an ab initio investigation of the twenty-four
low-lying doublet and quartet electronic states was carried out via
MRCI (+Q) method. The PECs and DMCs for all the obtained states
have been determined, along with the TDMs among the lowest
allowed doublet and quartet electronic states. The reduction of
the core-approximation in the inner-shell correlation active space,
that is included in the CI calculations, can improve the results. The
spectroscopic constants Te , xe , xe xe , Be , ae , Re , and De for fourteen
bound electronic states have been calculated. For several vibra-
tional levels, the eigenvalue Ev , the rotational constant Bv , the cen-
trifugal distortion constant Dv , and the abscissas of the turning
points Rmin and Rmax have been obtained. The Einstein coefficients,
the spontaneous radiative lifetime, the emission oscillator
strength, and some other constants are also calculated for the low-
est electronic transitions. Moreover, the FCFs have been deter-
mined for the lowest 2R+2R+ and 2R+2P electronic transitions
with a discussion on the feasability of the laser cooling of the NaBe
molecule. Twenty-two electronic states are investigated here for
the first time.
2. Ab initio calculations
The state-averaged molecular orbitals are generated by using
multi-configuration self-consistent field (MCSCF) method. This
generation is followed by the multireference configuration interac-
tion (MRCI + Q) technique to treat effectively the dynamical corre-
lation energy that arising from the coulomb repulsion between
electrons. These calculations have been performed by the compu-
tational chemistry program MOLPRO [39] using the graphical user
interface GABEDIT [40]. Both Be and Na atoms are treated as a sys-
tems with all electrons scheme by using cc-pwCV5Z basis set given
by Prascher et al. [41] for s, p, d and f atomic orbitals. To obtain bet-
ter results, a large active space has been identified in the C2v sym-
metry: 9r (Be: 2s, 2p0 , 3s; Na:3s, 3p0 , 4s, 3d0 , 4p0 , 5s), 4p (Be: 2p1;
Na: 3p1, 3d1, 4p1), and 1d (Na: 3d2) orbitals distributed into
irreducible representation in the C2v group: 10a1 , 4b1 , 4b2 , 1a2
noted by [10,4,4,1]. Thus, the Frozen Core Orbitals (FCO) include
1s of Be and 1s2s2p of Na, and 3 correlation electrons along with
19 active orbitals used in both MRCI and MCSCF calculations (first
FCO). The PECs and DMCs have been determined as function of the
internuclear distance R in the range 1:7 6 R 6 15 with a step of
0.02 . In addition, the TDMCs for the lowest electronic transitions
between different states have been calculated in the same range of
R. Moreover, the 2p atomic orbital of Na atom is opened in the
MRCI calculation to estimate the correlation effect of the inner-
shell electrons on the molecular properties, and to improve the
results. Consequently, the correlation energy calculations were
performed also with 9 active electrons and 22 active orbitals with
the orbitals of 1s of Be and 1s2s of Na are frozen core orbitals (sec-
ond FCO).
3. Results and discussion
3.1. PECs and spectroscopic parameters of ground and excited states of
NaBe molecule
The PECs correlating to the first set of frozen core orbitals (3
valence electrons and 19 active orbitals) for the 24 low lying dou-
blet and quartet electronic states are drawn in Figs. 1 and 2. It
should be noted that all investigated electronic states are almost
bound states except the (3)4R+ and (1)4D that are obviously repul-
sive states. Some crossings and avoided crossings between the
PECs at certain points can be also detected. In fact, the adiabatic
potential energy curves of two electronic states of the same quan-
tum number K of the electronic orbital angular momentum and
the same symmetry properties cannot cross each other. This result
of the two adiabatic solutions of the Schrdinger equation arising
from the mixed electronic states. Owing to the possibility of cross-
ing from one electronic state to another, such conical intersections
(crossing) can dramatically alter the stability of the molecule. In
addition, an incorrect chemical picture will emerge if such cross-
ings are overlooked [42]. Also, the transition state of a chemical
reaction can be characterized by the avoided crossing state [43].
Thus, the positions of the crossings Rc and avoided crossings Rac
along with their energy gap separation DEac are represented in
Tables 1 and 2. Moreover, the PECs for the lowest electronic states
(1)2P, (2)2R+, (1)4P and (1)4R+ that are obatined with the first and
second FCOs are plotted in Figure FS1 in Supplementary Material
file to show the effect of the inner-shell electrons correlation on
the PECs behavior. Obviously, the number of active electrons affect
the dissociation limits and the positions of the equilibrium inter-
nuclear distance of these curves, but the difference between the
dissociation limits which obtained by the two sets of FCOs is more
salient. In fact, the bonding in NaBe compound is van der Waals in
Fig. 1. Potential energy curves of the lowest 2R+, 2P, and 2D electronic states of the
NaBe molecule. The calculation has been done by using MRCI/MCSCF calculation
with 3 correlation electrons and 19 active orbitals. The frozen core orbitals include
1s of Be and 1s2s2p of Na.
 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341 35

Table 2
Avoided crossings positions and energy separation between different electronic states
of the molecule NaBe.

State1/State2 Rac () DEac (cm
1)

2 + 2 +
(3) R /(4) R 3.06 120.71
(4)2R+/(5)2R+ 2.50 2512.98
(5)2R+/(6)2R+ 8.02 1481.45
(6)2R+/(7)2R+ 2.86 175.58
(3)2P/(4)2P 3.54 2043.31
7.64 1501.20
(2)4R+/(3)4R+ 2.64 526.74
3.28 26.33
(3)4P/(4)4P 2.14 1951.13
(4)4P/(5)4P 1.84 1099.5
9.54 1448.16

the asymptotic region, but it can slightly change the equilibrium

bond distances in the van der Waals systems [44]. Consequently,
the spectroscopic parameters for the different bound electronic
Fig. 2. otential energy curves of the lowest 4R(+/
), 4P, and 4D electronic states of states have been calculated with the two sets of FCOs. Further-
the NaBe. The calculation has been done by using MRCI/MCSCF calculation with 3
more, the energy of the lowest dissociation limits of the investi-
correlation electrons and 19 active orbitals. The frozen core orbitals include 1s of Be
and 1s2s2p of Na. gated low-lying electronic states has been obtained based on the
two sets. By comparing with the NIST experimental data in litera-
ture [45], the correlation rules hold for the adiabatic potential
Table 1 curves of the low-lying electronic states and the results are
Positions of the crossings between the different elec- reported in Table 3. However, some dissociation limits of the high-
tronic states of the molecule NaBe.
est calculated molecular states are not obtained due to the undula-
State1/State2 Rc () tions in the PECs for these electronic states. In fact, the short-range
X2R+/(1)2P 1.94 electronic interactions are significant at certain energy points. They
(2)2R+/(1)2P 4.04 are related to the singularities in the electronic Hamiltonian oper-
(3)2R+/(2)2P 8.76 ator and giving rise to the Coulomb cusp in the electronic wave
(4)2R+/(3)2P 2.06
function and appearance of cusps in the exact wave function. Also,
4.60
5.62 these undulations are explained by the breakdown of the Born-
(5)2R+/(3)2P 2.72 Oppenheimer (B.O) approximation since the interactions between
3.82 electronic states are significant at certain energy points, and the
7.84 responsible term for the so-called non-adiabatic effects can be
(1)2D/(3)2P 2.00
(1)2D/(3)2R+ 1.74
very important and it cannot be neglected. According to the values
(1)2D/(4)2R+ 2.02 of Table 3, one valence electron of Na atom is excited (3s?3p) giv-
(1)2D/(5)2R+ 2.24 ing rise to two-doublet electronic states (2)2R+ and (1)2P at the
(5)2R+/(4)2P 2.08 second dissociation limit. In addition, one active electron of Be
(1)2D/ (4)2P 2.36
atom is excited (2s?2p) giving rise to two doublet states (3)2R+
(6)2R+/(4)2P 6.48
9.38 and (2)2P and two quartet states (1)4R+ and (1)4P at the third dis-
(1)2D/(6)2R+ 3.18 sociation limit. The same analysis can be extracted for the others
(1)4P/(1)4R
2.16 dissociation limits from the atomic configurations of Table 3. An
(1)4R+/(1)4R
2.92 obvious upward shift of the all-asymptotic energies can be shown
(2)4P/(1)4R
4.00
14.92
by the comparison between the dissociation energy values
(3)4P/(1)4R
7.72 obtained by the two calculations with different valence electrons
9.50 in Table 3. Moreover, the small relative error mentioned in Table 3
(2)4P/(1)4R+ 2.02 can also ensure the accuracy of the obtained PECs.
(1)4D/(3)4P 2.34
The spectroscopic parameters are obtained by fitting the calcu-
13.62
(1)4D/(2)4R+ 5.84 lated ab initio energy values of the different bound electronic
11.50 states, around the equilibrium internuclear distance Re, into a poly-
(3)4P/(2)4R+ 2.24 nomial in R. The electronic transition energy Te, the harmonic fre-
(3)4R+/(2)4R
2.30 quency xe, the anharmonic vibrational constant xe xe , the
(4)4P/(2)4R
6.88
(4)4R+/(2)4R
9.38
rotational constants Be and ae , the equilibrium internuclear dis-
(5)4P/(2)4R
10.30 tance Re and the dissociation energy De have been calculated for
(4)4P/(3)4R+ 2.2 the fourteen bound states. The results are displayed in Table 4.
(4)4P/(4)4R+ 2.82 Some of the others bound states are not presented in Table 4 since
4.14
their PECs are very shallow or have an avoiding crossing around
their equilibrium internuclear distance that prevent to generate
correctly the polynomial coefficients. It should be noted that the
origin and weak due to the diffuse alkali valence s orbitals [37]. The reduction of core-approximation plays obvious effect on the
electronic dynamical correlation promotes the dispersion forces spectroscopic constants. By comparing our theoretical parameters
effectively on well-separated systems. This dispersion effects, due values obtained for the considered states by the two calculations
to the temporary attraction between an induced dipoles, can play with different active electrons, the equilibrium internuclear dis-
a major role in the second set of FCO (9 active electrons) calcula- tances Re are slightly changed with relative differences range
tions. It can cause an upward shift of the dissociation energies in 0:07% 6 dRe =Re 6 5:63%. However, the relative differences become
36 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341

Table 3
Molecular orbitals of the NaBe molecule correlated to the lowest dissociation limits.

Configuration of Be + Na Experimental energies Molecular states Calculated energies of NaBe Relative error (%)
of Be + Na (cm
1) at long range distance (cm
1)
Be (1s22s2, 1S) + Na (2p63s, 2S) 0:00 X2R+ 0:00a 0:00a
0:00a1 0:00a1
Be (1s22s2, 1S) + Na (2p63p, 2P0) 16956:2 (2)2R+, (1)2P 15897:7a 6:24a0:04a1
16963:0a1
Be (1s22s2p, 3P0) + Na (2p63s, 2S) 21981:3 (3)2R+, (2)2P 22071:7a 0:41a
(1)4R+, (1)4P 22128:8a1 0:67a1
Be (1s22s2, 1S) + Na (2p64s, 2S) 25740:0 (4)2R+ 25771:3a 0:12a3:89a1
26741:1a1
2 2 1 6 2 0
Be (1s 2s , S) + Na (2p 4p, P ) 30267:0 (5)2R+, (3)2P 29850:8a 1:37a
31139:3a1 2:88a1
Be (1s22s2p, 3P0) + Na (2p63p, 2P0) 38934:4 (2)4R+, (3)4R+, (2)4P, (3)4P, (1)4R
, (1)4D 37970:8a 2:47a
39084:8a1 0:38a1
Be (1s22s2p, 3P0) + Na (2p64s, 2S) 47721:3 (4)4R+, (4)4P 47838:7a 0:24a
48860:2a1 2:38a1
a
Present work using MCSCF/MRCI method with 3 valence electrons (first FCO).
a1
Present work using MCSCF/MRCI method with 9 valence electrons (second FCO).

Table 4
The spectroscopic parameters and permanent dipole moment le for the X2R+ and thirteen excited states of the NaBe molecule based on first and second FCOs.
State T e (cm
1) xe (cm
1) xe ve (cm
1) Be (cm
1) ae 102 (cm
1) Re () De (cm
1) jle j (Debye)
2 + a a a a a a a
X R 0:00 163:8 11:48 0:281 1:069 3:041 1190:1 2:34a
0:00a1 158:3a1 12:37a1 0:286a1 1:188a1 3:015a1 1058:0a1 0:97a1
173:0b 2:970b 1291:0b 2:33b
164:0c1 3:052c1 1161:5c1
3:045c2 1024:3c2
(1)2P 6149:73a 338:4a 3:78a 0:392a 0:345a 0:342a1 2:576a 10938:1a 6:45a
6855:39a1 348:8a1 3:71a1 0:406a1 2:533a1 11170:0a1 5:61a1
(2)2R+ 10876:98a 237:9a 2:98a 0:293a 0:288a 2:981a 6210:8a 0:63a
11338:50a1 252:3a1 2:83a1 0:305a1 0:271a1 2:921a1 6682:5a1 2:00a1
(2)2P 18588:55a 126:4a 2:81a 0:227a 0:385a 3:384a 4673:2a 0:54a
19140:77a1 121:1a1 1:17a1 0:226a1 0:168a1 3:391a1 4065:2a1 0:84a1
(1)4P 20054:87a 223:5a 5:42a 0:307a 0:525a 2:909a 3204:2a 6:19a
20337:31a1 220:8a1 5:73a1 0:312a1 0:563a1 2:889a1 2849:6a1 5:25a1
(3)2R+ 21203:70a 106:0a 0:63a 0:169a 0:067a 3:920a 1:94a
21500:92a1 105:7a1 0:78a1 0:159a1 0:088a1 4:043a1 1:53a1
(1)4R+ 23205:99a 21:0a 1:47a 0:079a 0:387a 5:723a 60:7a 0:58a
23136:49a1 18:0b 5:727a1 48:8a1 0:66a1
5:840b 50:0b 0:45b
(1)4R+ 24434:49 334:9 1:90 0:423 0:390 2:480 14720:9 6:46
25269:73a1 342:4a1 3:71a1 0:436a1 0:377a1 2:444a1 14898:4a1 6:00a1
(3)2P 25736:43a 99:1a 0:01a 0:109a 4:896a 7:56a
26551:23a1 112:1a1 0:02a1 0:122a1 4:620a1 7:57a1
(2)4P 31620:18a 162:0a 0:89a 0:235a 0:086a 3:327a 7535:3a 0:24a
32373:09a1 176:7a1 0:89a1 0:248a1 0:079a1 3:240a1 7769:8a1 0:67a1
(1)2D 32032:14a 279:4a 5:32a 0:373a 0:525a 2:643a 4364:8a 3:36a
33178:03a1 281:8a1 5:45a1 0:382a1 0:547a1 2:610a1 4351:1a1 1:75a1
(3)4P 37929:81 121:7a 4:77a 0:202a 0:514a 3:589a 1227:9a 1:33a
38849:36a1 125:8a1 5:36a1 0:210a1 0:567a1 3:521a1 1307:7a1 1:12a1
(4)4P 44432:17a 77:4a 0:02a 0:078a 5:780a 12:63a
46089:69a1 79:9a1 0:07a1 0:087a1 5:460a1 9:27a1
(4)4R+ 44664:18a 171:6a 0:62a 0:212a 0:038a 3:499a 6:53a
45216:65a1 179:6a1 0:43a1 0:219a1 3:450a1 7:28a1
a
Present work using MCSCF/MRCI method with 3 valence electrons (first FCO).
a1
Present work using MCSCF/MRCI method with 9 valence electrons (second FCO).
b
Theoretical values calculated by Pototschnig et al. [31] using MRCI method with 3 valence electrons.
c1
Theoretical values calculated by Bauschlicher et al. [37] using CASSCF/MRCI method with 3 valence electrons.
c2
Theoretical values calculated by Bauschlicher et al. [37] using SCF/MCPF (including the 2s2p inner-shell correlation of Na atom) method.

larger for the dissociation energies De where 0:03% 6 dDe =De 6
19:60% which is because of the effect of long-range induced
dipole-induced dipole attraction. For the ground state X2R+, our
calculated spectroscopic parameters using the first FCO are in very
good agreement with the theoretical values of Ref. [37] using
CASSCF/MRCI method with 3 valence electrons where the
relative differences are dRe =Re 0:36%, dxe =xe 0:12% and
dDe =De 2:40%. These small errors between the values are
because of the inclusion of the valence s and p orbitals only in
the active space of Bauschlicher et al. [37] calculation whereas a
large active space is adopted in our calculation with the selection
of a different basis. However, the relative difference of the dissoci-
ation energy De becomes larger (dDe =De 13:93%) when Bauschli-
cher et al. [37] used the SCF/MCPF method including the 2s2p
inner-shell correlation of Na atom, but the equilibrium bond dis-
tance Re slightly varies and the discrepancy becomes
dRe =Re 0:13%. It should be noted that the relative difference of
the dissociation energy decreased from 13.93% to 3.18% when the
 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341
number of active electrons of the inner-shell has been increased in
our calculation (second FCO), whereas the relative difference of the
bond distance Re slightly increased from 0.13% to 0.99%. The values
of our spectroscopic constants (first FCO calculation) are in
good agreement with those calculated by Pototschnig et al. [31]
with relative differences dRe =Re 2:33%, dxe =xe 5:61% and
dDe =De 8:48% for the X2R+ ground state. Moreover, the differ-
ence between our harmonic frequency value (xe 21:0 cm
1 ) of
the (1)4R+ and the theoretical value of Ref. [31] (xe 18:0 cm
1 )
is about 3:0 cm
1 , as well as the discrepancy between the Re values
is dRe =Re 2:04%. For this state, the difference is about 10:7 cm
1
between the dissociation energy values, but it is decreased to
1:2 cm
1 by using the second FCO in our calculation. These differ-
ences between the values are due to the selection of a different
number of atomic orbitals functions of the quintuple-zeta basis,
and a different number of active orbitals. Thus, there is an overall
good agreement between our calculated parameters for the first
doublet and quartet R+ electronic states with those available in
the literature. This feature can ensure the accuracy of our spectro-
scopic values for the higher doublet and quartet excited states that
are calculated by the same way. Future experimental studies can
confirm this prediction.
3.2. Permanent and transition dipole moments, and radiative lifetimes
of NaBe molecule
The uneven and non-uniform distribution of charges between
the two atoms of a heteropolar molecule leads to a permanent
dipole moment l. The quantum mechanical operator of the perma-
nent electric dipole moment (PEDM) is a simple sum of one-elec-
tron operators. Thus, it can be among the most reliably predicted
physical properties [46]. In addition, a large value of the magnitude
of the PEDM is useful to align molecules in an optical lattice, and to
study long-range dipoledipole forces [47,48]. At the MRCI level,
the permanent dipole moments (PDMs) for the considered low-
est-lying doublet and quartet electronic states, using the first set
of FCOs, as functions of internuclear distance R are plotted in Figs. 3
and 4. As a general trend, the DMCs for the most considered elec-
tronic states smoothly tend to zero at large R, as it is expected for
neutral compound. However, the DM curves of the (6)2R+, (7)2R+,
(4)2P and (2)4R
are not displayd at large R due to the cusps in
the electronic wavefunctions which are explained above. One can
Fig. 3. Permanent dipole moment curves of the lowest 2R+, 2P, and 2D states of the
NaBe molecule. The calculation has been done by using MRCI/MCSCF calculation
with 3 correlation electrons and 19 active orbitals. The frozen core orbitals include
1s of Be and 1s2s2p of Na.
37
Fig. 4. Permanent dipole moment curves of the lowest 4R(+/
), 4P, and 4D states of
the NaBe molecule. The calculation has been done by using MRCI/MCSCF calculation
with 3 correlation electrons and 19 active orbitals. The frozen core orbitals include
1s of Be and 1s2s2p of Na.
notice that the abrupt crossing between two different DMCs, corre-
sponding to two electronic states of the same quantum number K
and in the same symmetry, occurs at the same position Rac of the
avoiding crossing between the PECs corresponding to these two
states. In this case, the polarity of the two atoms is reversed and
the electronic character is interchanged in this region. The Rac posi-
tions are mentioned in Table 2 for whole crossings between differ-
ent DMCs. This agreement between positions is a good sign for the
accuracy of our calculated excited states. The PDMs have been cal-
culated by taking the beryllium (Be) atom at the origin, and the
sodium (Na) atom moves along the positive z-axis. We adopt the
following sign convention for DM values, a positive dipole moment
indicates that the vector of the DM points from the Be atom to the
Na atom. In this case, the center of negative charges being closer to
the Be atom than the center of positive charges, and in the case of a
negative value of DM indicates that the center of electron charges
is closer to the Na atom than the center of positive charges. Far
from those electronic states that have an avoiding crossing, the
X2R+, (1)2P, (1)4P, (1)4R
states have positive dipole moments,
and the (1)4R+, (1)4D quartet states have a negative value along
the distance R. But, the states (2)2R+, (2)2P, (1)2D, (2)4P, (2)4R

and (4)4R+ have a change in sign of the DM values with
respect to R. In the first set of FCOs calculation, the dipole
moment curve of the ground state has a maximum point
R 2:40 ; l 3:19 D, and the DMC of (1)4R+ shows a mini-
mum pointR 2:44 ; l
4:57 D. But the maximum of the
X2R+ changes to the another point R 2:32 ; l 2:65 D, and
also the (1)4R+ dipole moment curve exhibits different minimum
R 2:48 ; l
4:56 D with the second FCO calculation. Fur-
thermore, the calculated DMCs of lowest doublet and quartet
states X2R+, (1)2P, (2)2R+, (1)4P and (1)4R+ with the first and sec-
ond FCOs are displayed in Figure FS2 in Supplementary Material
file. As a result of this comparison, the number of valence electrons
can effectively affect the magnitude of the dipole moment. This is
due to a significant influence of the core correlation electrons on
the DM value [49,50]. Thus, the PDM values have been calculated
at the equilibrium bond distance, jle j, using the two sets of FCOs,
and are given in Table 4. Our calculated jle j of the ground state
X2R+, as obtained from the first FCO calculation, shows an
excellent agreement with the value calculated by Pototschnig
38 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341

et al. [31] where the relative difference is dle =le 0:42%, but the
agreement becomes less for the (1)4R+ state and the difference
between jle j values is about 0.13 Debye. It should be noted that
our calculated values of jle j for the ground state can be useful to
study the long-range dipoledipole interactions. It is known that
the polarity of molecules is amplified when the electronegativity
difference between atoms is large. The difference in electronegativ-
ity between the two atoms A and B is obtained according to Paul-
q
ings definition as jvA
vB j DAB
DA2 DB2 1=2 , where DAB ; DA2 ; DB2
are the dissociation energies of the diatomic molecules AB, A2 and
B2 , respectively Ref. [50]. It is clear that the value of the dipole
moment le of the ground state decreased significantly with the
increasing value of the valence electrons. This can be explained
by the electronegativity difference between two atoms. Since De
of the ground state decreased by the increasing value of the active
electrons from 3 to 9, the polarity of molecule is attenuated. Con-
sequently the second FCO calculation is more reliable for the cor-
rect description of the van de Waals interaction in NaBe molecule.
The transition dipole moments (TDMs) for the transitions from
the lowest-excited doublet states ((1)2P, (2)2R+, (2)2P, (3)2R+,
(3)2P) to the ground state as a function of the internuclear distance
are plotted in Fig. 5 based on the first set of FCO. Moreover, the
TDM curves of the allowed transitions among the lowest excited
states can be found in Figure FS3 in the Supplementary Material.
One can notice that the most of the TDMCs vanish when R is larger
than 9 due to spin forbidden transitions between two atomic
orbitals at asymptotic limits. For example, the dipole moments of
the X2R+(2)2P and X2R+(3)2R+ transitions tend to zero at large
R due to the forbidden transition from Be (1S) to Be (3P). However,
the allowed transition from Na (2S) to Na (2P) give a constant val-
ues of the TDMs for the X2R+(1)2P, X2R+(2)2R+ and X2R+(3)2P
transitions when R is larger than 8. The significant value, 6:66 D
obtained with the first FCO or 6.51 calculated with the second
one, of the dipole moment for the X2R+(2)2R+ transition at large
R can be useful for laser cooling applications. In addition, the TDMC
of (1)4P(1)4R+ transition has a small values since the (1)4R+ state
is weakly bound, and the TDMC of X2R+(3)2R+ exhibits a strong
variations at short distances which are related to strong configura-
tion interaction along with a sudden change at R  3:06 due to
the avoided crossing between (3)2R+ and (4)2R+ states. Also, Figs. 5
and FS3 (in supplementary material) show sudden changes and
jumps in some TDMCs at different internuclear distances, which
can be explained by the radialionless electronic transitions (no
change in spin). These transitions are most probable when two
potential energy curves cross or come very close to one another,
and they happen without an appreciable alteration of energy and
position of the nuclei. Then, the electronic motion suddenly
switches from one electronic state to another, and the electronic
wavefunctions of these states are mixed. It should be noted that
for diatomic molecules, a radiationless process is significant when
the transition occurs from a certain electronic state to another dis-
sociated electronic state. At R larger than the crossing point
Rc 4:04 between the (2)2R+ and (1)2P, a radialionless transi-
tion can take place around this crossing region. Due to this effect,
the TDMCs of the X2R+(1)2P and X2R+(2)2R+ transitions exhibit
a sudden change at the crossover point which is located at the
internuclear distance ( 4:28 , and an abrupt changes in the
TDMCs of the (1)2P(2)2P, (1)2P(3)2P and (2)2R+(3)2R+ transi-
tions occur at the same position ( 4:28 . A radialionless elec-
tronic transition can occur in the region of the crossing
(4:60 6 R 6 5:62 between the two electronic states (3)2P
and (4)2R+, and leads to an abrupt changes in the TDMCs for the
transitions of the (1)2P, (2)2P and X2R+ with (3)2P state at
R  4:78 . Due to the suddenly switches of the electronic motion
between the crossing states (3)2P and (5)2R+, a sudden jumps
occur for the TDMCs of (1)2P(3)2P and (2)2P(3)2P transitions.
The TDMs among the electronic states along with the DMs of them
can be useful for many experiments mentioned in the introduction.
In fact, the expectation value of PEDM operator is sensitive primar-
ily to the nature of the least energetic and most chemically rele-
vant valence electrons [46]. Consequently the TDMs values at
equilibrium position Re of the upper state for the considered elec-
tronic transitions have been obtained with the first and second
FCOs calculations. Moreover, the emission coefficients for the low-
est allowed electronic transitions are also calculated by using our
obtained data along with the relations of Hilborn [51]. For the sake
of brevity, only the TDM value jl21 j, the radiative lifetime s21 and
the oscillator strength constant jf 21 j of the lowest transitions,
based on the second set of the FCOs, are presented in Table 5.
While the radiative lifetimes of the lowest-excited doublet elec-
tronic states (2)2R+, (2)2P, (3)2R+, (3)2P are given in Table 6. How-
ever, these constants that are obtained with the first set of the FCOs
along with others which are calculated by using the two sets of
FCOs, are collected in Tables TS1 and TS2 in the Supplementary
Material. From Tables 5 and 6, one can find that the lowest quartet
states have longer lifetimes than the lowest doublet electronic
states, and the largest jl21 j values belong to the (2)2P(3)2P and

Table 5
Calculated transition dipole moment jl21 j, radiative lifetime s21 and oscillator
strength jf 21 j based on the second set of FCOs for the lowest electronic transitions.

Transition jl21 j(a.u.) s21 (ns) jf 21 j

2 + 2
X R (1) P 0:670 3422:8 0:0093
(1)2P(2)2R+ 0:836 7862:1 0:0095
X2R+(2)2R+ 2:894 40:5 0:2885
(2)2R+(2)2P 0:825 1534:0 0:0161
(1)2P(2)2P 2:236 53:3 0:1866
X2R+(2)2P 1:606 27:3 0:1501
(2)2P(3)2R+ 0:414 218859:6 0:0012
(2)2R+(3)2R+ 1:519 204:3 0:0712
(1)2P(3)2R+ 0:366 1178:6 0:0059
X2R+(3)2R+ 1:054 44:7 0:0726
(1)4P(1)4R+ 0:088 2886060:3 0:00007
(1)4P(1)4R
0:119 290515:9 0:0002
(3)2R+(3)2P 0:295 44201:6 0:0013
(2)2P(3)2P 3:036 131:8 0:2075
Fig. 5. Transition dipole moment curves between the ground state X2R+ and the
(2)2R+(3)2P 0:703 284:4 0:0228
lowest-excited doublet states of the NaBe molecule. The calculation has been done
(1)2P(3)2P 2:388 11:3 0:3414
by using MRCI/MCSCF calculation with 3 correlation electrons and 19 active
X2R+(3)2P 0:456 126:8 0:0168
orbitals. The frozen core orbitals include 1s of Be and 1s2s2p of Na.
 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341
Table 6
The calculated radiative lifetime of the (2)2R+, (2)2P, (3)2R+,
(3)2P electronic states using the second set of FCOs.
State sspon (ns)
(2)2R+ 40:3
(2)2P 17:9
(3)2R+ 35:6
(3)2P 9:3
X2R+(2)2R+ transitions. These transitions and the (1)2P(3)2P
transition have the largest oscillator strength and take place in
the infrared region. No comparison could be done for our TDMs
and emission coefficients values with any experimental or theoret-
ical data, since they are provided here for the first time.
In order to support the reliability of our work, we represent in
Table 7 the values of the transition coefficients A21, jf 21 j, S21 and
k21 for the X2R+(2)2R+ and X2R+(1)2P transitions at long inter-
nuclear distance by using the values of the transition dipole
moment l21 and the angular frequency x21 given in Table 7. At this
range, the Na atom is the responsible species for these transitions
according to table 3. The comparison of our calculated values with
those available in NIST database [45] for Na atom shows a very
good agreement.
3.3. The vibrationrotation calculation
The vibrational energy Et , the rotational constant Bt , and the
centrifugal distortion constant Dt are obtained by solving, within
the BornOppenheimer approximation (B.O), the radial Schrdin-
ger equation of nuclear motion using the canonical functions
approach [5254], and the cubic spline interpolation between each
two consecutive points of the PECs. Moreover, the abscissas of
turning points Rmin and Rmax are also obtained by using the values
of the vibrational energies with the ab initio PECs. In the first FCO
calculation, the values of these constants for X2R+, (1)2P, (2)2R+,
(2)2P, (1)4P, (1)4R+, (1)4R
, (2)4P and (3)4P are reported in
Table TS3 in the Supplementary Material. These constants are not
calculated for the other bound states due to the breakdown of
the B.O approximation at the position of crossings or avoided
crossings of the PECs that belong to the same symmetry. Moreover,
the ro-vibrational constants for the ground state and some other
states are also calculated using the second set of the FCOs to exam-
ine the effect of the number of active electrons on these constants.
For the sake of brevity, the vibrational levels of X2R+ and (2)2R+
based on the 9 valence electrons calculation are given in Table 8,
and those of (1)2P and (1)4P electronic states are collected in
Table TS4 in the Supplementary Material. From Tables 8 and TS3,
one can find that the vibrational energies Et of the ground state
decrease with the increase of the number of valence electrons that
are similar to that of KBe molecule [33]. Also, the number of vibra-
tional levels change with the number of active electrons. These
demonstrate the significant effect of the number of correlation
electrons on the vibrational levels. There are no data in literature
Table 7
Calculated values of the emission Einstein coefficients A21 , wavelength k21 , oscillator strength jf 21 j and line strength S21 for the X2R+ (2)2R+ and X2R+(2)2R+(1)2 transitions at
long distance.
Transition (12) jl21 j (a.u.) x21  10
15 (rads
1)
2 + 2 + a a
X R (2) R 2:62 2:99
X2R+(1)2P 2:56a1 3:19a1
a
Present work by using MCSCF/MRCI method with 3 valence electrons.
a1
Present work by using MCSCF/MRCI method with 9 valence electrons.
b
NIST database For Na atom Ref. [45].
39
to compare it with our results, since these ro-vibrational constants
are given here for the first time.
3.4. Discussion of the laser-coolability of the NaBe molecule
The values of the FCFs, which describe the overlap of the vibra-
tional wave functions for the spontaneous radiative transitions, are
essential to identify the optimal electronic transition for laser cool-
ing. By using the LEVEL8.2 program [55], the FCF values have been
obtained for X2R+(2)2R+, X2R+(1)2P and (1)2P(2)2R+ transi-
tions based on the two sets of FCOs. For the sake of brevity, the
FCFs of spontaneous radiative transitions, f t0 t , between 0 6 t0 6 9
of the upper state and 0 6 t 6 9 of the lower state are only dis-
played. Also, the results of the first set are given in Table TS5 in
the Supplementary Material, in addition the results of the second
FCO calculation are reported in Table TS6. However, The FCF values
of X2R+(2)2R+ transition, using the second set of FCOs, are also
illustrated in Fig. 6. Table TS6 exhibits a small values of the diago-
nal FCFs, in which f 00 0:004 for the X2R+(1)2P, and f 00 0:012
for the (1)2P(2)2R+ transition. Also, the largest value among the
diagonal FCFs are 0:093 and 0:137 which belong to (1)2P
t0 2 M X2R+ t 2 and (2)2R+ t0 1 M (1)2P t 1
respectively.
Therefore, the NaBe compound cannot be cooled by laser
through these transitions. Fig. 6 displays a large diagonal FCF for
the (2)2R+ t0 0 M X2R+ t0 transition with
f 00 0:822andasmalldiagonalvaluesfort P 1. It should be noted
that the (2)2R+ t0 0 M X2R+ t 1 has a significantly off-diagonal
non-negligible FCF value (f 01 0:166). Based on the straightfor-
ward features of the potential energy curves in Fig. 1 and the off-
diagonal FCFs for the lowest electronic transitions, the main crite-
rion of laser cooling is not verified for NaBe molecule. Therefore,
the NaBe compound is unsuitable candidate for laser cooling.
4. Conclusion
In the present work, the PECs and DMs of the NaBe molecule
have been studied theoretically for the low-lying 24 doublet and
quartet electronic states via MCSCF/ MRCI technique, with the suit-
able basis set cc-pwCV5Z. This study has been performed with dif-
ferent frozen core orbitals, and different numbers of valence
electrons. Taking advantage of the ab initio PECs of the investigated
electronic states, the spectroscopic constants Te , xe , xe ve , Be , ae ,
Re , De have been calculated for the most of the bound electronic
states. Moreover, the ro-vibrational constants Ev , Bv , Dv along with
the abscissas of turning points Rmin and Rmax have been obtained for
different vibrational levels of the NaBe molecule. It is found that
the number of active electrons has an obvious effect on the
molecular properties. The present molecular spectroscopic values
are in very good agreement with those available in the literature.
The TDMs, the spontaneous radiative lifetime and some other
coefficients have been determined for the lowest allowed
electronic transitions. To the best of our knowledge, twenty-two
new electronic states have been studied here for the first time.
A21  10
7 (s
1) k21 (nm) jf 21 j S21 (a.u)
a a a
5:57 629:5 0:332 13:7a
6:46a1 589:9a1 0:337a1 13:1a1
6:14b 589:6b 0:320b 12:4b
40 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341

Table 8
Values of the eigenvalue Et , the rotational constants Bt and Dt , and the abscissas of the turning points for the different vibrational levels of X2R+ and (2)2R+ based on the second
FCO calculation.

State K2R+1 v Ev cm
1 ) Bv  10 cm
1 ) Dv  106 cm
1 ) Rmin () Rmax ()

2 +
X R 00 77.39 2.8063 3.9466 2.857 3.226
1 222.45 2.6867 4.3958 2.766 3.429
2 354.17 2.5598 4.9463 2.713 3.606
3 472.57 2.4266 5.618 2.675 3.781
4 577.83 2.2876 6.3891 2.647 3.964
5 670.4 2.1436 7.2409 2.624 4.160
6 750.89 1.9940 8.2441 2.607 4.374
7 819.89 1.8391 9.3226 2.593 4.613
8 878.18 1.6805 1.0687 2.581 4.882
9 926.45 1.5159 12.0702 2.572 5.197
10 965.82 1.3606 12.8178 2.565 5.549
11 997.73 1.2034 15.096 2.560 5.960
12 1022.73 1.0445 17.9277 2.555 6.454
13 1041.34 0.8690 24.9193 2.552 7.080
(2)2R+ 0 124.2 3.0203 1.7929 2.792 3.082
1 370.8 2.9922 1.7836 2.702 3.206
2 614.74 2.9657 1.8081 2.643 3.297
3 855.4 2.94 1.8027 2.597 3.375
4 1093.03 2.9122 1.7642 2.559 3.446
5 1328.04 2.8831 1.7759 2.527 3.512
6 1560.16 2.8551 1.8082 2.498 3.575
7 1789.04 2.8266 1.7886 2.473 3.636
8 2014.81 2.7963 1.7733 2.450 3.695
9 2237.45 2.7655 1.813 2.429 3.752
10 2456.68 2.735 1.8393 2.409 3.809
11 2672.34 2.7033 1.8223 2.391 3.866
12 2884.43 2.6699 1.8348 2.375 3.923
13 3092.84 2.6359 1.8902 2.359 3.979
14 3297.3 2.6016 1.925 2.344 4.036
15 3497.64 2.5656 1.9275 2.331 4.093
16 3693.77 2.5278 1.9523 2.318 4.152
17 3885.56 2.489 2.0162 2.306 4.211
18 4072.79 2.4497 2.0661 2.294 4.271
19 4255.36 2.4093 2.0723 2.283 4.333
20 4433.24 2.368 2.0709 2.273 4.395
21 4606.46 2.3256 2.137 2.264 4.458
22 4774.77 2.2804 2.329 2.254 4.525
23 4937.42 2.2285 2.6058 2.246 4.596
24 5093.32 2.1694 2.7829 2.238 4.671
25 5241.9 2.1072 2.8578 2.230 4.753
26 5383.02 2.0415 3.0862 2.223 4.840
27 5516.22 1.9706 3.2856 2.217 4.935
28 5641.18 1.8968 3.5312 2.211 5.037
29 6052.35 1.5392 5.7789 2.192 5.558

Fig. 6. The calculated FCFs of the NaBe molecule for the lowest 10 vibrational levels of the transitions X2R+(2)2R+. The calculation has been done by using MRCI/MCSCF
calculation with 9 correlation electrons and 22 active orbitals. The frozen core orbitals include 1s of Be and 1s2s of Na.

The distributed FCFs have been calculated for the transitions electronic transitions, the NaBe molecule cannot be considered a
X2R+(2)2R+, X2R+(1)2P and (1)2P(2)2R+ of NaBe. Based on laser-cooled candidate. Nevertheless, further investigations and
the off-diagonal Franck-Condon factors for the considered lowest experimental works are needed for this molecule.
 W. Chmaisani et al. / Chemical Physics 491 (2017) 3341
Acknowledgements
The authors would like to acknowledge the use of the Ankabut
High Power Computer Facility Cluster and the Khalifa University
High Power Computer shared facility, Abu-Dhabi UAE. Also, the
authors would like to thank the Lebanese National Council for Sci-
entific Research for the financial support of the present work by
the grant program for scientific research 2013-2015.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemphys.2017.
04.007.
References
[1] K.M. Jones, E. Tiesinga, P.D. Lett, P.S. Julienne, Rev. Mod. Phys. 78 (2006) 483
536.
[2] T. Khler, K. Gral, P.S. Julienne, Rev. Mod. Phys. 78 (2006) 13111362.
[3] E.A. Donley, N.R. Claussen, S.T. Thompson, C.E. Wieman, Nature (London) 417
(2002) 529.
[4] C.A. Regal, C. Ticknor, J.L. Bohn, D.S. Jin, Nature 424 (2003) 47.
[5] K.E. Strecker, G.B. Partridge, R.G. Hulet, Phys. Rev. Lett. 91 (2003) 080406.
[6] C.A. Stan, M.W. Zwierlein, C.H. Schunck, S.M.F. Raupach, W. Ketterle, Phys. Rev.
Lett. 93 (2004) 143001.
[7] S. Inouye, J. Goldwin, M.L. Olsen, C. Ticknor, J.L. Bohn, D.S. Jin, Phys. Rev. Lett.
93 (2004) 183201.
[8] Jeremy M. Sage, Sunil. Sainis, Thomas. Bergeman, David. DeMille, Phys. Rev.
Lett. 94 (2005) 203001.
[9] D. Wang, J. Qi, M.F. Stone, O. Nikolayeva, H. Wang, B. Hattaway, S.D. Gensemer,
P.L. Gould, E.E. Eyler, W.C. Stwalley, Phys. Rev. Lett. 93 (2004), 243005.
[10] J. Weinstein, R. de Carvalho, T. Guillet, B. Friedrich, J.M. Doyle, Nature 395
(1998) 148.
[11] D. Egorov, J.D. Weinstein, D. Patterson, B. Friedrich, J.M. Doyle, Phys. Rev. A 63
(2001) 030501(R).
[12] D. Egorov, W.C. Campbell, B. Friedrich, S.E. Maxwell, E. Tsikata, L.D. van
Buuren, J.M. Doyle, Eur. Phys. J. D 31 (2004) 307311.
[13] Boerge Hemmerling, Eunmi Chae, Aakash Ravi, Loic Anderegg, Garrett K.
Drayna, Nicholas R. Hutzler, Alejandra L. Collopy, Jun Ye, Wolfgang Ketterle,
John M. Doyle, arXiv:1603.02787v1 [physics.atom-ph] 9 Mar 2016.
[14] E.S. Shuman, J.F. Barry, D. DeMille, Nature 467 (2010) 822.
[15] T.A. Isaev, S. Hoekstra, R. Berger, Phys. Rev. A 82 (2010), 052521.
[16] N. Wells, I.C. Lane, Phys. Chem. Chem. Phys. 13 (2011) 19018.
[17] I.C. Lane, Phys. Chem. Chem. Phys. 14 (2012) 15078.
[18] S.Y. Kang, Y.F. Gao, F.G. Kuang, T. Gao, J.G. Du, G. Jiang, Phys. Rev. A 91 (2015)
042511.
[19] R. Yang, Y.F. Gao, B. Tang, T. Gao, Phys. Chem. Chem. Phys. 17 (2015) 1900.
[20] Y.F. Gao, T. Gao, Phys. Rev. A 90 (2014) 052506.
[21] Yang You, Chuan-Lu Yang, Mei-Shan Wang, Xiao-Guang Ma, Wen-Wang Liu,
Phys. Rev. A 92 (2015) 032502.
[22] M.T. Hummon, M. Yeo, B.K. Stuhl, A.L. Collopy, Y. Xia, J. Ye, Phys. Rev. Lett. 110
(2013) 143001.
41
[23] V. Zhelyazkova, A. Cournol, T.E. Wall, A. Matsushima, J.J. Hudson, E.A. Hinds, M.
R. Tarbutt, B.E. Sauer, Phys. Rev. A 89 (2014) 053416.
[24] T.V. Tscherbul, R.V. Krems, Phys Rev Lett 97 (8) (2006) 083201.
[25] J.J. Hudson, B.E. Sauer, M.R. Tarbutt, E.A. Hinds, Phys Rev Lett 89 (2) (2002)
023003.
[26] D. Kawall, F. Bay, S. Bickman, Y. Jiang, D. DeMille, Phys. Rev. Lett. 92 (2004),
133007-1-4.
[27] J. Prez-Ros, F. Herrera, R.V. Krems, New J. Phys. 12 (2010) 103007.
[28] Phys. DeMille, Rev. Lett. 88 (2002) 067901.
[29] A. Micheli, G.K. Brennen, P. Zoller, Nat Phys 2 (5) (2006) 341347.
[30] G. Pupillo, A. Griessner, A. Micheli, M. Ortner, D.W. Wang, P. Zoller, Phys Rev
Lett 100 (5) (2008) 050402.
[31] J.V. Pototschnig, A.W. Hauser, W.E. Ernst, Phys. Chem. Chem. Phys. 18 (2016)
5964.
[32] Chuan-Lu Yang, Yang You, Xiao-Guang Ma, Mei-Shan Wang, Li-Zhi Wang,
Wen-Wang Liu, J. Quant. Spectrosc. Radiat. Transfer 165 (2015) 5667.
[33] Ke-La Xiao, Chuan-Lu Yang, Mei-Shan Wang, Xiao-Guang Ma, Wen-Wang Liu,
J. Chem. Phys. 139 (2013) 074305.
[34] Alexander I. Boldyrev, Jack Simons, Paul von R. Schleyer, J. Chem. Phys. 99
(1993) 8793.
[35] Svetlana Kotochigova, Alexander Petrov, Maria Linnik, Jacek Kos, Paul S.
Julienne, J. Chem. Phys. 135 (2011) 164108.
[36] R. Schlachta, I. Fischer, P. Rosmus, V.E. Bondybey, Chem. Phys. Lett. 170 (1990)
485491.
[37] C.W. Bauschlicher Jr., S.R. Langhoff, H. Partridge, J. Chem. Phys. 96 (1992) 1240.
[38] P.J. Bruna, F. Grein, Mol Phys 100 (11) (2002) 16811691.
[39] H.-J. Werner, P.J. Knowles, G. Knizia, F.R. Manby, M. Schutz, P. Celani, T. Korona,
R. Lindh, A. Mitrushenkov, G. Rauhut, K.R. Shamasundar, T.B. Adler, R.D. Amos,
A. Bernhardsson, A. Berning, D.L. Cooper, M.J.O. Deegan, A.J. Dobbyn, F. Eckert,
E. Goll, C. Hampel, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Koppl, Y.
Liu, A.W. Lloyd, R.A. Mata, A.J. May, S.J. McNicholas, W. Meyer, M.E. Mura, A.
Nicklas, D.P. ONeill, P. Palmieri, D. Peng, K. Pfluger, R. Pitzer, M. Reiher, T.
Shiozaki, H. Stoll, A.J. Stone, R. Tarroni, T. Thorsteinsson, M. Wang, version
2012.1, a package of ab initio programs, 2012, see <http://www.molpro.net/
info/users>.
[40] A.R. Allouche, Gabedit a graphical user interface for computational chemistry
softwares, J. Comput. Chem. 32 (2011) 174182.
[41] B. Prascher, D.E. Woon, K.A. Peterson, T.H. Dunning Jr., A.K. Wilson, Theor.
Chem. Acc. 128 (2011) 69.
[42] D.G. Fedorov, S. Koseki, M.W. Schmidt, M.S. Gordon, Int. Rev. Phys. Chem. 22
(2003) 551.
[43] S. Shaik, A. Ioffe, A.C. Reddy, A. Pross, J. Am. Chem. SOC. 116 (1994) 213262.
[44] Stefan. Grimme, Peter R. Schreiner, Angew. Chem. Int. Ed. 50 (2011) 12639.
[45] <www.nist.gov/pml/data/asd.cfm>.
[46] T.C. Steimle, Int. Rev. Phys. Chem. 19 (2000) 455477.
[47] J. Deiglmayr, M. Aymar, R. Wester, M. Weidemueller, O. Dulieu, J. Chem. Phys.
129 (2008) 064309.
[48] G. Gopakumar, M. Abe, M. Hada, M. Kajita, J. Chem. Phys. 140 (2014) 224303.
[49] W. Mller, W. Meyer, J. Chem. Phys. 80 (1984) 33113320.
[50] D.A. Fedorov, A. Derevianko, S.A. Varganov, J. Chem. Phys. 140 (2014) 184315.
[51] R.C. Hilborn, Am. J. Phys. 50 (1982) 982, Revised version (2002).
[52] M. Korek, H. Kobeissi, Can. J. Phys. 73 (1995) 559565.
[53] M. Korek, H. Kobeissi, J. Comput. Chem. 13 (1992) 11031108.
[54] M. Korek, Comput. Phys. Commun. 119 (1999) 169178.
[55] A computer program for solving the radial Schrdinger equation for bound and
quasibound levels, J. Quant. Spectrosc. Radiat. Transfer (2016), http://dx.doi.
org/10.1016/j.jqsrt.2016.05.028.