An isomeric study of N

5
, N
5
, and N

5
: a Gaussian-3
investigation
Xin Wang
a
, Hai-rong Hu
a
, Anmin Tian
a
, N.B. Wong
b
, Siu-Hung Chien
c
,
Wai-Kee Li
c,
*
a
Department of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
b
Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, People's Republic of China
c
Department of Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong, People's Republic of China
Received 20 June 2000; in nal form 21 August 2000
Abstract
An isomeric study for N
5
Y N

5
, and N

5
has been carried out using the Gaussian-3 (G3) method. At the MP2(FU)/6-
31G(d) level, six N
5
, ve N

5
, and four N

5
isomers are identied. Of these 15 species, 12 of them have not been reported
previously. The most stable N
5
isomer is a weak N
2
N
3
complex with C
2v
symmetry, while the most stable N

5
isomer
is also a weak N
2
N

3
complex with the same symmetry. The most stable species for N

5
has an open-chain structure
with C
2v
symmetry, which has been synthesized and characterized spectroscopically. Natural bond orbital (NBO)
analysis suggests that the stability of this cation is enhanced by hyperconjugation. 2000 Elsevier Science B.V. All
rights reserved.
1. Introduction
Polynitrogen compounds N
n
and their ions
have attracted considerable research interest re-
cently. As early as 1992, Bartlett and co-workers
studied the stability and energetics of N
4
Y N
6
, and
N
8
using SCF, coupled-cluster, and many-body
perturbation theory methods. In this work [1], four
N
4
isomers (with symmetries T
d
Y C
s
Y C
2v
, and
D
2h
), one N
6
isomer (D
6h
), and one (cubic) N
8
isomer were found. Four years later, Schleyer et al.
[2] applied DFT methods to investigate a large
number of (mostly neutral) nitrogen clusters,
ranging from n = 4 to n = 20, with n mostly being
an even number. For the isomers of a given n
value, these researchers identied the most stable
one. In 1997, Schaefer et al. [3] found two addi-
tional N
8
isomers (with symmetries D
2h
and C
2v
).
One year later, Li and co-workers [4] carried out
an isomeric study for N
7
and eight isomers were
found. Among them, only four have reasonable
stability and the most stable isomer has a twisted
open-chain structure. More recently, Klap otke [5]
applied SCF, MP2, and CCD methods to study
the open-chain diazide (N
6
) molecule.
The results described so far are entirely theo-
retical in nature and they await experimental
conrmation. On the other hand, one of the rst
experimental evidences for the existence of an N
n
species with n b 3 was reported last year. In this
27 October 2000
Chemical Physics Letters 329 (2000) 483489
www.elsevier.nl/locate/cplett
*
Corresponding author. Fax: +852-26035057.
E-mail addresses: suqcp@mail.sc.cninfo.net (A. Tian),
bhnbwong@cityu.edu.hk (N.B. Wong), wkli@cuhk.edu.hk
(W.-K. Li).
0009-2614/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 0 ) 0 1 0 7 1 - X
work, Christe et al. [6] synthesized the compound
N

5
AsF

6
. In addition, based on their calculations
carried out at the CCSD(T)/6-311+G(2d) level, the
authors proposed that the cation N

5
has an open-
chain structure with C
2v
symmetry. This structural
proposal was supported by the agreement between
the calculated and experimental (IR/Raman and
NMR) spectroscopic measurements. Later that
year, Li et al. [7] performed an ab initio and DFT
study on the mechanism of the formation of the
N

5
cation. Earlier this year, Nguyen and Ha [8]
carried out another ab initio and DFT study on
N

5
. In addition to the aforementioned species with
C
2v
symmetry, they also found a triplet structure
corresponding to a weak complex between linear
triplet N

3
and N
2
. This triplet species is less stable
than the singlet structure with C
2v
symmetry by
about 26 kJ mol
1
. Furthermore, they suggested
that the radical N
5
also has an open C
2v
form in
which the two terminal nitrogens point inward
instead of outward as in the N

5
cation. The ion-
ization energy (IE) is estimated to be 7X4 0X2 eV.
In addition, it is noted that Maier et al. [9] as-
signed discrete absorptions of the N

3
cation ob-
served between 245 and 283 nm to the
A
3
P
u
X
3
R

g
transition. Related to this work,
Maier et al. [10] observed the photoabsorptions by
a series of N

3
(N
2
)
n
(n = 16) complexes near 282
nm. In the Letter by Nguyen and Ha [8], the sin-
glettriplet energy gap between states
3
R

g
and
1
R

g
for N

3
is reported as 1.4 eV. On the other hand,
the corresponding values calculated by Cai et al.
[11] (and cited by Maier et al. [9]) are 1.45 eV for
3
R

1
D and 2.12 eV for
3
R

1
R

. Note that these

two sets of results are based on dierent geome-
tries for N

3
X D
h
symmetry for Nguyen and Ha
[8] and C
v
for Cai et al. [11]. We have carried out
preliminary work on this cation, optimizing its
structure at the CI levels of MP2 (full), CASSCF
(4,6), CCSD(T), and QCISD using the 6-31G(d)
basis set as well as at the DFT level of B3LYP/6-
311 +G(3df). For the rst two levels of theory, we
obtained an asymmetric structure with C
v
sym-
metry. For the remaining three levels of theory, the
equilibrium structure has the D
h
symmetry. In
addition, by carrying out Gaussian-3 (G3) calcu-
lations based on the QCISD/6-31G(d) geometry,
we were able to reproduce the singlettriplet
energy gap of 1.40 eV reported by Nguyen and Ha
[8]. Obviously, more work needs to be done in this
regard. However, since the main aim of the current
project is concerned with the N
5
isomers and its
singly charged cations and anions, we will not deal
with the N

3
cation any further in this Letter.
Since N

5
is the only N
n
(n b 3) species with
synthetic and spectroscopic evidence, we con-
centrate on the structures and energetics of the
N

5
isomers in this work. In addition, we also
study the N
5
and N

5
isomers. The theoretical
model we employ is the recently proposed G3
method [12]. Comparison between our results
with those obtained by other workers will also
be made.
2. Method of calculation and results
All calculations were carried out on various
DEC workstations as well as on SGI Origin 2000
High Performance Server, using the GAUSSIAN AUSSIAN98
package of programs [13].
The computational method we employed was
the aforementioned G3 model of theory. In this
method, the structure of a species is optimized at
the MP2(FU)/6-31G(d) level. The G3 model is an
approximation for the theoretical level of
QCISD(T,FU)/G3large, where G3large is a basis
set specially designed for this model [12]. Fur-
thermore, MP2(FU)/6-31G(d) vibrational fre-
quencies, scaled by 0.9661 [14], are applied for the
zero-point vibrational energy correction at 0 K.
The G3 heats of formation at temperature T
(DH
fT
) in this work were calculated in the follow-
ing manner. For molecule AB, its G3 DH
fT
was
calculated from the G3 heat of reaction DH
rT
(AB AB) and the respective experimental
DH
fT
(A) and DH
fT
(B) for elements A and B. In
the calculations for anions, the DH
fT
for a free
electron was set to zero.
In addition to the structural and energetics re-
sults, the bonding in the various isomers identied
will also be discussed using natural bond orbital
(NBO) analysis [15,16].
In our notation, single- or double-digit numer-
als with superscript + or such as 7

and 12

refer to stable N

5
cations and N

5
anions, respec-
484 X. Wang et al. / Chemical Physics Letters 329 (2000) 483489
tively. Those numerals without any superscript
such as 1 refer to stable N
5
isomers. All structures
identied have only real vibrational frequencies.
The structures of various N
5
(16), N

5
(7

11

), and N

5
(12

15

) isomers optimized at
the MP2(FU)/6-31G(d) level are shown in Fig. 1.
Also shown in this gure for reference are the
structures optimized at the B3LYP/6-311+G(3df)
level. The heats of formation DH
f0
and DH
f298
of all
isomers are summarized in Table 1. Based on these
results, the IEs and electron anities (EAs) of all
N
5
isomers can then be easily calculated and they
are tabulated in Table 2.
3. Discussion
As shown in Fig. 1 and Table 1, six N
5
isomers,
ve N

5
isomers, and four N

5
isomers have been
identied. We will discuss the structures, energet-
ics, and bonding of these isomers in three sections:
radicals rst, followed by cations and anions.
Fig. 1. The structures of N
5
Y N

5
, and N

5
isomers. The levels of optimization are MP2(FU)/6-31G(d) (normal font) and B3LYP/6-
311+G(3df,2p) (bold font). Note that 2 is not found at the B3LYP level. Also, while the MP2 vibrational frequencies for all species are
real, 3, 6, and 10

have one imaginary vibrational frequency each at the B3LYP level.

X. Wang et al. / Chemical Physics Letters 329 (2000) 483489 485
3.1. The N
5
isomers
The most stable N
5
isomer is 1 with C
2v
sym-
metry. As suggested by its structure shown in
Fig. 1, 1 may be considered as a symmetric weak
complex between fragments N
3
and N
2
, with the
distance between N
1
and N
4
being larger than 3
#
A.
At the G3 level, the dissociation energy for 1 to
fragment into N
3
and N
2
is 15 kJ mol
1
. This
negative value arises from the fact that geometry
optimization and energy calculation were not
carried out at the same theoretical level. To get a
better estimate of this dissociation energy, we
performed geometry optimization at the
MP2(FU)/6-311+G(3df,2p) level and the dissoci-
ation was then calculated to be 5 kJ mol
1
. Hence,
it is safe to say that this complex is a weak one,
both structurally and energetically. In terms of
NBO analysis, there is a triple bond between N
4
and N
5
, and there are delocalized double bonds
linking atoms N
1
Y N
2
, and N
3
. As a result of this
picture, there is a net positive charge on N
1
(+0.16)
Fig. 1. (Continued).
486 X. Wang et al. / Chemical Physics Letters 329 (2000) 483489
Table 1
The G3 total energies (E
0
)
a
and enthalpies (H
298
), and the standard heats of formation at 0 and 298 K (DH
f0
and DH
f298
) of isomeric
N
5
Y N

5
and N

5
Species Symmetry E
0
H
298
DH
f0
DH
f298
(Hartree) (kJ mol
1
) (kJ mol
1
) (kJ mol
1
)
N
5
1
b
C
2v
273X52064 273X51306 518.9 517.4
2 C
s
273X45552 273X44991 689.9 683.2
3 C
2v
273X43289 273X42773 749.3 741.4
4 C
2v
273X28750 273X28322 1131.0 1120.8
5 D
2d
273X27838 273X27345 1155.0 1146.4
6 D
3h
273X15544 273X15112 1477.8 1467.6
N

5
7

C
2v
273X15849 273X15304 1469.8 1462.6
8

D
2d
272X97523 272X97000 1950.9 1943.2
9

C
2v
272X93720 272X93127 2050.8 2044.8
10

C
4v
272X90844 272X90330 2126.3 2118.3
11

D
3h
272X77697 272X77240 2471.4 2462.0
N

5
12
b
C
2v
273X64224 273X63484 199.7 197.6
13

D
5h
273X61729 273X61313 265.2 254.6
14

C
s
273X53356 273X52701 485.0 480.7
15

D
2d
273X34160 273X33682 989.0 980.1
a
The G3 electronic energy reported here is corrected with MP2(FU)/6-31G(d) frequencies, scaled by 0.9661.
b
The G3 E
0
values for N
2
Y N
3
, and N

3
are )109.49761, )164.02877, and )164.15470 Hartrees, respectively. From these results, it can
be calculated that the dissociation energy (DE) for 1 N
2
+ N
3
is 15 kJ mol
1
, and the DE for 12

N
2
+ N

3
is )26 kJ mol
1
.
These DEs become positive when both geometry optimizations and energy calculations are carried out at the same level, such as
MP2(FU)/6-311+G(3df,2p) (see text).
Fig. 1. (Continued).
X. Wang et al. / Chemical Physics Letters 329 (2000) 483489 487
and negative charges on N
2
and N
3
(0X08). Also,
since the separation (3.139
#
A) between N
1
and N
4
exceeds slightly the van der Waals interaction
distance (~3.08
#
A) for two nitrogen atoms, the
interaction between N
1
and N
4
appears to be es-
sentially electrostatic in nature, with the natural
atomic charge on N
4
being about 0X02.
About 170 and 230 kJ mol
1
less stable than 1
are, respectively, isomers 2 (C
s
symmetry) and 3
(C
2v
). (Isomer 2 was found at the MP2(FU)/6-
31G(d) level, but not at the B3LYP/6-
311+G(3df,2p) level.) NBO analysis for these two
structures does not yield any novel bonding fea-
tures. It should be noted that 3 has been found by
Nguyen and Ha [8], while the more stable isomers
1 and 2 have not been reported in the literature.
Also, the structural features of 3, as shown in Fig.
1, agree with the qualitative description given by
Nguyen and Ha. Upon ionization, all three radical
isomers 13 yield cation 7

, the most stable N

5
isomer with C
2v
symmetry. The G3 IE for 3 is 7.47
eV, in good agreement with that estimated by
Nguyen and Ha [8], 7X4 0X2 eV.
The remaining three N
5
isomers, 46, have
fairly symmetrical structures. However, they are
all highly energetic species, about 610960 kJ
mol
1
less stable than 1. In view of their instability,
there will be no further discussion for these iso-
mers. They are reported here for reference only.
3.2. The N

5
isomers
The most stable N

5
isomer is 7

with the open-

chain structure (C
2v
symmetry). This is the most
studied N

5
cation, as well as the only one found in
the literature, both experimentally [6] and com-
putationally [68]. NBO results suggest that the
two terminal NN bonds are triple bonds. In ad-
dition, there are strong donoracceptor interac-
tions between lone pair orbitals on N
1
and the p
+
orbitals of the two triple bonds. Furthermore,
there are also donoracceptor interactions between
the lone pair orbital on N
4
(or N
5
) and the r
+
orbital on N
1
N
2
(or N
1
N
3
). In other words, the
stability of this cation is enhanced by hypercon-
jugation, as concluded by Klap otke [5].
The remaining four N

5
isomers, 8

11

, are all
of fairly high symmetry. They are also highly en-
ergetic, about 5001000 kJ mol
1
less stable than
7

. Due to their instability, there will be no further

discussion for these isomers. However, it should be
noted that cations 8

Y 9

, and 11

arise from the

ionization of N
5
isomers 5, 4, and 6, respectively.
3.3. The N

5
isomers
Among the four N

5
isomers shown in Fig. 1,
only the one with cyclic structure, 13

, has been
reported in the literature [2]. However, according
to the G3 results, the aromatic anion 13

is not the
most stable N

5
isomer. Rather, 12

lies lower in
energy by about 65 kJ mol
1
. Examining the
structure of 12

, as well as its NBO results, this

anion may been taken as a weak complex between
N

3
and N
2
. At the G3 level, the dissociation en-
ergy for the process 12

3
N
2
is calculated
to be 26 kJ mol
1
. Once again, this small nega-
tive value arises from the fact that geometry op-
timization and energy calculation were not done at
the same theoretical level. To better estimate this
dissociation energy, we performed geometry opti-
mization at the MP2(FU)/6-311+G(3df,2p) level.
Table 2
The G3 IEs and EAs of N
5
isomers
Isomer IE EA
Energy (eV) Process Energy (eV) Process
1 9.85 1 7

3.31 12

1 e

2 8.08 2 7

5.08 12

2 e

3 7.47 3 7

4 9.53 4 9

6.70 14

4 e

5 8.25 5 8

1.72 15

5 e

6 10.30 6 11

488 X. Wang et al. / Chemical Physics Letters 329 (2000) 483489
At such a level, the dissociation energy becomes 10
kJ mol
1
. Hence, as in the case of N
5
isomer 1, 12

is also a weak complex which may dissociate eas-

ily. NBO results suggest that there is a triple bond
between N
1
and N
2
, and there are two double
bonds linking atoms N
3
Y N
4
, and N
5
. As a result,
there is net positive charge on N
4
(+0.23) and
negative charges on N
3
(0X63) and N
5
(0X60),
while N
1
and N
2
are essentially neutral. The
binding between N
2
and N

3
moieties in 12

may
be considered as weak van der Waals interaction,
as the separation (3X032
#
A) between N
3
and N
1
(or
N
2
) is slightly smaller than the van der Waals in-
teraction distance (~3.08
#
A) for two nitrogen at-
oms.
About 220 kJ mol
1
less stable than 13

is
isomer 14

. According to its NBO results, this

anion may be taken as a complex between N
2
and
a nearly cyclic N

3
moiety. Natural atomic charges
indicate most of the negative charge of this anion
resides on N
1
and N
2
(0X45 each). The least
stable N

5
isomer is 15

. It is less stable than 12 by

nearly 800 kJ mol
1
. It is included here for refer-
ence only.
Finally, it is noted that, upon attaching an extra
electron to radical 1 and 2, anion 12

is formed.
On the other hand, attaching an electron to 3 and
4 would lead to the formation of 14

and 15, re-

spectively.
4. Conclusion
Applying the G3 method, we have carried out
an isomeric study for N
5
Y N

5
, and N

5
. At the
MP2(FU)/6-31G(d) level, six N
5
, ve N

5
, and four
N

5
isomers are identied. Out of these 15 species,
12 of them are introduced for the rst time.
The most stable N
5
isomer is 1, which may be
considered as a weak N
3
N
2
complex with C
2v
symmetry. The energy for dissociating 1 into two
fragments is only a few kJ mol
1
and the interac-
tion between the two fragments is electrostatic in
nature. The most stable species for N

5
is 7

, a
cation that has been synthesized and characterized
spectroscopically. NBO analysis suggests that the
stability of this cation is enhanced by hypercon-
jugation. The most stable N

5
isomer is 12, a weak
complex of the form N
2
N

3
having C
2v
sym-
metry. The dissociation energy for this anion is
estimated to be 10 kJ mol
1
.
Also reported are the DH
f
values and the
structures of all 15 species, as well as the IEs and
EAs of the N
5
isomers. NBO analysis is carried out
for the more stable species found.
Acknowledgements
This project is supported by the National Sci-
ence Foundation of China (project No.
298730029). NBW is grateful to the City Univer-
sity of Hong Kong for the award of a Strategic
Grant (account no. 7000939). WKL acknowledges
the support of a Direct Grant (account No.
2060146) from the Chinese University of Hong
Kong.
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