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Abstract: A detailed exploration of the singlet potential surface for the system CHNO has been carried out with the aid of ab
initio molecular orbital theory with minimal, split-valence, and split-valence polarization basis sets. Direct search procedures are used to locate minima and transition states within the surface. The most stable isomer of CHNO is predicted to be
isocyanic acid (HNCO) followed by cyanic acid (HOCN), formonitrile oxide (HCNO), and carboxime (HONC). Each of
these isomers is predicted to be quite stable with respect to intramolecular rearrangement. HCNO is found to have a linear
equilibrium geometry while HNCO, HOCN, and HONC are each predicted to have trans bent structures. It is shown that singlet formyl nitrene and the cyclic isomers of CHNO are unlikely to be observable species. The rearrangement of HCNO to
HNCO proceeds via structures resembling oxazirine and formylnitrene; however, neither of these species is predicted to be an
intermediate on the reaction path.
One of the simplest typical organic molecules-containing the typical organic elements carbon, hydrogen, nitrogen, and oxygen-is the molecule with the empirical formula CHNO. Although reasonable valence structures may be
drawn for a t least seven CHNO isomers (Table I), relatively
little is known experimentally about these compounds. Only
two isomers, H N C 0 2and H C N 0 , 3 have been isolated in pure
form and subjected to detailed spectroscopic examination. The
substituted isomers R N C 0 , 4 R C N 0 , j and ROCN4 are more
common, and substituted formylnitrenes R C ( 0 ) N have frequently been invoked as reactive intermediates6 Theoretical
information on the CHNO isomers is equally scarce. Half a
century ago, Pauling and Hendricks used a simple electrostatic model to predict the relative energies of HCNO and
H O N C . Since then, theoretical investigations have been limited to selected isomers and a b initio calculations have been
reported for isocyanic acid,s-10 formonitrile oxide, two cyclic
CHNO isomers,I2 and f ~ r m y l n i t r e n e . ~ ~ . ~
In the present work, we use a b initio molecular orbital theory
to systematically examine the various C H N O isomers, their
geometries, their electronic strxtures, their energetic relationships, and the reaction pathways which interconvert them.
Among the 38 possible, topologically different, bound C H N O
isomers we focus our attention on the 12 potentially stable
species 1-12 and various bridged structures (see below) which
1.
-&N
C-NKH
\ /
10
-.
ti-C-0-N
II
A+
-C
12
may serve as transition states in intramolecular rearrangements. Our aim is to treat all stable isomers and transition
states a t uniform levels of sophistication rather than to generate
high-quality wave functions for a few selected species. We hope
that our study will facilitate subsequent applications of more
sophisticated techniques to specific regions of interest.
Computational Methods. For all molecules considered in this
paper, the wave function of the lowest singlet state was approximated by a single determinant of 11 real, doubly occupied
molecular orbitals. The spatial form of these orbitals was optimized by the LCAO-MO-SCF technique introduced by
Journal of the American Chemical Society
7807
Table I. Structures and Names of CHNO Isomers
Molecule
Structure
Name
1
2
3
4
Isocyanic acid
Cyanic acid
Formonitrile oxide
Carboximea
Formylnitrene
Oxazir ine
HN=C=O
HOCTN
HC=N-O
HON=C
H-C, / / O
N
A
Q
,
H-N-C
H-C=N
10
Oxaziridinylidene
distance in H C N O has recently been interpreted as the projection of a C-H bond length of 1.061 8, upon the heavy-atom
Formonitrile Oxide (3).This molecule is computed to be 80
kcal mol- (6-31G*/4-31G) less stable than the most stable
isomer isocyanic acid (1). Compared with the rs structure derived from microwave spectra,38the computed N - 0 and C-H
bond lengths are too large. Minimal and double [basis set
calculations also overestimate the length of the dative N - 0
3b
30
(8:Iao. + = l a 0 1
c f BIDII
14-31G, CmvI
Cmvl
ISTO-3G.
3c
(p:3 6 2 0 ,
(8;180, 4: I801
3O6O3l
bond in amine oxide^.'^,^^ Normal N - 0 bonds, however, appear to be described quite well by the STO-3G basis: the
axis of a quasi-linear molecule.42This model leads to an HCN
angle of approximately 165 and an inversion barrier of about
0.1 kcal mol-. Our theoretical results do not support this
conclusion. Constraining the H C N angle in H C N O at 165
but optimizing all other bond lengths and angles leads to an
energy
increase of 0.85 kcal mol- (STO-3G). Thus, the theIsocyanic Acid (1). According to our best (4-31G, 6-31G*)
oretical
equilibrium structure of H C N O is Cmo.
calculations, isocyanic acid (HNCO) is the most stable C H N O
Carboxime (4). We predict that this molecule is less stable
isomer. This result seems to conform with available experithan its tautomer formonitrile oxide (3) by 2 kcal mol- (6mental evidence: isocyanates are often the final products in
31G*/4-31G). As in the case of H N C O and HOCN, the opattempts to generate other C R N O isomers. Previous ab initio
timum structure is trans bent and planar. The theoretical C-N
calculations on isocyanic acid have been carried out at experimental or model geometries using minimal8 or e ~ t e n d e d ~ , ~ ~
,
H
H
,
,
o%b958
basis sets. The best experimental structure^^^,^^ for H N C O
C-N
O
-L
c=As7+
have, in turn, been derived from microwave spectral data assuming a linear N C O chain. Our calculations suggest, however, that the N C O group is nonlinear. Both the STO-3G and
*25
383
I75
00,
lO)j+/
I342
I62
I72 b
Ib
IO
18:29.
9~3551
(STO-3G.
C,l
IC
( @ = I O . 0.3581
(4-31G. C,l
I69
( p = 4~8 0 ,
cf e i p l l 2 07DN1
4-3 1G calculations support earlier C N D 0 / 2 results35in predicting a trans bent equilibrium structure for HNC0.36From
studies of small triatomic hydrides,22it is well known that the
4-3 1G basis set is biased in favor of linear as opposed to angular
structures. That we find, even at the 4-3 1G level, a trans bent
equilibrium geometry therefore strongly indicates that the
N C O group in H N C O is in fact bent. Experimental verification of this result would be highly desirable.
Cyanic Acid (2). We find cyanic acid (HOCN) to lie 21 kcal
mol- (6-31G*/4-31G) above H N C O (1). As in the case of
isocyanic acid, the optimum structure is calculated to be trans
bent. The optimum STO-3G and 4-31G C-N bond lengths are
slightly longer than in H C N (STO-3G, 1.153
4-31G,
4d
r2s
3993\.y
,
0-C=N
I59
09:&+y7
35057Q7=N
20
(8:153, + = 3 5 8 l
(STO-IG,
C,I
,,oi
50
H
,142
%T
2b
( 8 = 1 5 6 , 03591
(4-31G. C.1
\O---C=N
+IsL2o
-23
2c
( p 2 8901
C=N-0-H-CGN-0-H
5b
H-O-C3N-H-O=C=N
26
5c
5d
( 8 = 1 0 5 . 9.3371
ISTO-3G.
l p = l5501
C,l
7808
Table 11. Total Energies of Minima and Fragmentation Products
Total energy. hartrees
Molecule
STO-3G/STO-3G
4-3 1G /STO-3G
4-3 1G/4-3 1G
-165.502 92
-165.511 98
-165.392.21
-165.441 45
-165.391 46
-165.369 19
-165.406 29d
b
-165.391 58
-165.404 06d
-165.361 36
-165.337 03
-165.306 26
- 167.484 70
-167.497 27
-167.464 29
-167.370 12
-167.369 28
b
-167.334 91
b
- 167.307 05
b
-167.288 68
-167.329 54
-165.312 16
-167.297 01
2
3
4
5
6
7
8
9
10
N H COe
H C N Of
H N C Og
+
+
+
-167.457
-167.367
-167.365
-167.345
-167.325
-167.312
39
59
45
19
79
03d
b
-167.296
-167.279
-167.327
-165.311
-167.295
10
46d
00
43
83
6-31G*/4-31Ga
-167.754
-167.720
-167.627
-167.624
17
51
20
68
C
C
c
C
C
C
C
Not a minimum at this level. Not examined at this level. From ref 12.
a At optimum 4-31G geometry with linear heavy atom chain.
Optimum STO-3G (4-31G) bond lengths are, in A: r(N-H) = 1.079 (1.028);r(C-0) = 1.146 (1.128). fr(C-H) = 1.070 (1.051); r(C-N)
= 1.153 (1.140). g r ( N - H ) = 1.011 (0.979);r(N-C) = 1.170(1.162).
19.
90
( 8 ~ 6 7 9. ~ 7 1 1
(STO- 3 G )
i e = i e , +:io]
6b
18.17, + = 1 6 i
I S T O - 3 G . C,l
14-310, Csl
60
9b
l p = 2 OBDI
6c
( p : l 4401
Oxazirine (7). Oxazirine is isoelectronic with the antiaromatic cyclopropenyl anion and might therefore be expected
to distort to a nonplanar structure or to decrease its antiaromaticity by lengthening one or several bonds. Using the
STO-3G basis set, one finds a planar structure (7a) with a
0
($472
7b
ip=26~01
70
18.151, 4 . 2 9 9 1
I S T O - 3 G . C,l
100
1'502
IOb
18=30.+=3071 1 8 . 2 6 , + = s o 1
ISTO-3Gl
8a
18=11. +=2611
1 4 - 3 1 G . C.1
-15
IOC
i p = i 4701
14-31GI
7809
120'
160'
240'
CNO BOND ANGLE (9)-
600
300"
360"
Figure 1. STO-3G potential energy surface for CHNO. Contour labels are in kcal mol-' relative to the energy of the fully optimized HOCN structure
(2a), the lowest point on the STO-3G surface.
LLQ? !&h
Molecule
1
2
3
4
5
6
7
8
9
10
C-N
NH
j/>
13
+ CO
+0
+0
HCN
HNC
14
convention that the C-N bond be always written from the left
to the right, and that $(C-N-O) and the projection of
B(H-C-N) on the C N O plane be measured clockwise. Thus,
we have for 13 0 = 90, 4 = 300', whereas 14 is defined by 0
= 90, I$ = 60'.
The STO-3G potential energy surface is shown in Figure
1. This contour plot44is based on 274 distinct values of E(0,
4), each of which is a minimum with respect to the four remaining variables r(C-N), r ( N - 0 ) , r(C-H), and O(H-C,
N-O).45 The 4-31G surface (Figure 2) is based on 274 single
extended basis set calculations at these partially optimized
STO-3G geometries (cf. Table V). Note that the energies of
the minima which can be extracted from the 4-3 1G surface do
not exactly correspond to either the 4-31G/STO-3G or the
4-31G/4-31G levels. It is only if STO-3G and 4-31G predictions for r(C-H), r(C-N), r ( N - 0 ) , and O(H-C, N - 0 ) were
identical that the energies of the minima would agree precisely
with the values shown in Table 11.
On the STO-3G surface (Figure 1) there are six rather deep
minima corresponding to isocyanic acid (1) (0 N 30, 4 N O'),
cyanic acid (2) (0 N 150, 4 N O'), formonitrile oxide (3) (0
= 180', 4 N 180'), carboxime (4) (0 N 20, 4 170'),
oxazirine (7) (0 = 150, 4 N 300'), and oxaziridinylidene
(10) (0 N 30, 4 N 305'). The minima corresponding to 9 (0
70, 4 70') and 5 (0 N 105', 4 N 335') are less than
10 kcal mol-I deep and therefore not visible on the contour
plot. There are only four significant minima (1-4) on the
Re1 energy,
kcal mol-l
Level
0.0
21.1
19.1
81.3
81.5
101.9
108.4
119.4
118.3
130.9
105.3
116.2
125.1
6-3 1G*/4-3 1G
6-31G*/4-3 1G
6-3 1G*/4-3 1G
6-3 1G*/4-3 1G
4-3 1G/STO-3G
4-3 1G/4-3 1G
4-31G/STO-3G
4-3 1G/4-3 1G
4-31G/STO-3G
4-31G/4-31G
4-3 1G/4-31G
4-3 1G/4-3 1G
4-3 1G/4-3 1G
7810
0"
120"
180"
CNO BOND ANGLE
240"
60"
300"
360"
(+I-
Figure 2.4-31G potential energy surface for CHNO. Contour labels are in kcal mol-' relative to E(0, O), the lowest calculated point on the 4-31G/STO-3G
contour surface. The more important structures are superimposed on the surface.
H-c~N-0
/H
15
C=N
17
8 ' O
18
19
20
25
26
27
28
29
30
33
<H
STO-3G/STO-3G
-165.341
-165.369
-165.385
-165.279
-165.299
-165.387
-165.370
-165.302
4-31G/STO-3G 4-31G/4-31G
01
01
03
56
66
48
34
45
-167.317
-167.327
-167.352
-167.250
-167.180
-167.312
-167.305
-167.220
a
a
-167.252 78
b
35
43
83
03
-167.307 52
-165.319 09
- 167.226 09
-167.304 36
-167.286 00
-165.324 66
-167.293 91
O=C=N
-167.318 03
47
01
82
92
-.
99:24
-5
1795
! 157
1793
1144
HEFF'N
H&F'N
48;..,*iZ
095
15a
(8.180, 0 . 2 6 5 1
(STO-3G,
C.1
H-C3N
3 3 i ~j 2~196
.
;
0~,
111 .,,
,,(
'4
-I6
'0
15b
(8.179, 9.2741
(4-31G, C.!
I5c
(pz285D)
7811
(7) a t 8 = 180, 4 = 256' (STO-3G) or 8 = 179', 4 = 273'
(4-31G). With very long C - 0 and N - 0 bonds, a n essentially
linear H C N group, and a C-N bond typical of triple bonds,
this transition state resembles a weak complex between hydrogen cyanide and an oxygen atom. At the single determinant
level, it is bound with respect to H C N 0 by 4 kcal mol-'
(4-31G/4-31G) and lies 33 kcal mol-' (4-31G/4-31G) above
formonitrile oxide. According to the Woodward-Hoffmann
rules,46 the interconversion of the azide and triazirinyl anions
via the Czc transition state 16 is a thermally forbidden process.
'.
Path A
16
Although it is uncertain whether such arguments can be applied to the interconversion of the less symmetrical isoelectronic
formonitrile oxide and oxazirine molecules, there may be a
residual "symmetry" barrier of this kind which causes the C-0
and N - 0 bonds in 15 to be so weak. Furthermore, the lowest
singlet state of the free oxygen atom is not well described by
a single determinant of doubly occupied real orbitals. Part of
this error is presumably also present in the single determinant
wave function for weak complexes between an oxygen atom
and closed-shell molecules such as HCN. These considerations
weaken our conclusions regarding the structure and relative
energy of 15 and emphasize the desirability of multiconfiguration calculations for this part of the surface.
The second transition state on path A, 17, links the oxazirine
,
:&y7
,
,Ot
nL
190
18:52. 4.1971
I S T O - 3 0 . C.1
*I2
362
C -N
2591:
,;"~,, 1 :
Hkr9-:d
0'
,,,,'
17b
+:3191
19c
19b
18.57, +:I951
l 4 - 3 1 G , C.1
i+:2
25DI
The reaction scheme in Figure 3 suggests that a n edgeprotonated oxazirinyl anion 20a could serve as a transition state
0
-24
I70
18:135.
L
,
REACTION COORDINATE -
,H.
I p = 260Dl
ISTO-3G, C.1
(STO-3G/STO-3G) above the three-membered ring. However, the 4-3 1G calculations, carried out a t the optimum
STO-3G geometries, place 17 9 kcal mol-' below oxazirine
(7) and hence suggest that there is no barrier between oxazirine
(7) and formylnitrene (5).
The last transition state on the STO-3G path A is the hydrogen-bridged structure 18. On our contour surface, this point
200
1,.
20b
(8:64. +-2931
lSTO-3G)
*9
H~
, ,731 ~..!:33
1
p+7$,
I80
18:80, +:346)
ISTO-3G.
20c
Ip:109DI
1 ~~.~~
-2;A2--?
18b
Ip.1 2 I D )
C, I
-.
7812
According to our calculations, however, neither oxazirine nor
formylnitrene are true intermediates.
The Carboxime-Cyanic Acid Rearrangement. Carboxime
H O N C (4) and fulminates R O N C have never been positively
identified in the laboratory. Since our calculations suggest that
carboxime (4) and formonitrile oxide (3) are of comparable
thermodynamic stability, it is of interest to examine the kinetic
stability as well and to study theoretically the reaction channels
which connect carboxime with its more stable C H N O isomers.
We begin with the rearrangement to cyanic acid (2).
It is tempting to speculate that this reaction involves, either
as an intermediate or as a transition state, the oxygen-protonated oxazirinyl anion 9. Our STO-3G contour surface
(Figure 1) does show a valley which can be associated with
such a reaction path. This path sets out at 0 N 20, r#I N 180"
and leads via an intermediate 9 at B N 7 0 , 6 N 70" (which
is not visible in the plot because of the wide spacing of contour
lines) into the cyanic acid minimum at B N 150, r#I N 0". The
first transition state 25 on this route lies only 3 kcal mol-'
20
I/
M.
C.= N
80
d
a
40
[-CrN-0
Ob
+23
REACTION C O O R D I N A T E
ooo4V7'
cLl\l
90;,.,o;.~~6
492
I236
21
23
22
(01
R=(CH,l,C,
ICH,l,C/CH
(bl R=Ph
24
has proceeded further than the migration of R. This corresponds roughly to the high-energy route C in Figures 3-5. Our
best reaction path (A) is similar to Grundmann's earlier
suggestion:SS
R-C-N-0
R-C=N
/"\
R-Y0
R-N=C=O
N'
f31
FU
0-17
I' I'
C=N
II
-23
*I7
25a
2S b
( 8 . 5 2 . +:071
ip:l 7801
ISTO-3GI
??.?
260
18'97, + - 5 3 1
ISTO-30 I
+23
26c
26b
( 8 . 7 8 , 9.631
(4- 3101
( p r l 70Dl
- r~1
c=N
-R-CFN
I41
7813
H
C=N-0'
20
20
___-
4-31G
STO-3G
H
'
'C=N
\ 0/
C
C-N/Hd
'd
60
R E A C T I O N COORDINATE
A search for the transition state for the first step in this process
yielded a saddle point 28 with a geometry and energy quite
,
L 302
13
CCN---H
2054
2 258
0
I
C=N
28a
( a m i .# = 2 6 8 i
14-31G, C.1
H
. ' ?!.I.
t20
"......O
155\1;;"'
-10
\ 1',
jl 4 9 8
c
-
"-N
C=N
I258
t2
-12
27a
27b
i8:117. # a 7 7 1
I S T O - 3 G , C,)
1F:l 8 4 0 )
close to that of nitronylidene itself. W e were not able to explicitly demonstrate that 28 links 4 and 8 on the C H N O surface but its structure and energy as a transition state for the
transformation 4 -,8 are consistent with data in our 4-31G
contour surface (Figure 2). This point is not particularly important for our purposes here since examination of Figure 2
also indicates that the highest point on the reaction path is
almost certainly the second transition state 19 linking 8 and
3. This leads to a barrier of 73 kcal mol-l (4-31G/4-31G) for
the pathway shown in eq 6.
The Carboxime-Isocyanic Acid Rearrangement. The
third-and most stable-CHNO isomer into which carboxime
might rearrange is isocyanic acid (1). As in the case of the
formonitrile oxide-isocyanic acid isomerization, one may
postulate several reaction paths (Figure 7) which differ in the
phase of the oxygen and hydrogen movements. Many of the
individual steps in these reaction sequences have been discussed
above in connection with other rearrangements. This is the case
for the whole of path A. The highest barrier for this path is the
transition state 27 linking 9 and 7 and which lies 91 kcal mol-'
(4-31G/STO-3G) above carboxime.
An alternative path (B) involves, in 9, a migration of the
hydrogen atom from oxygen to nitrogen. The resulting oxaziridinylidene (10) could then presumably open the ring and
collapse to isocyanic acid (1). On the STO-3G surface, we find
a saddle point 29 which connects the minima associated with
29a
19.32,
#=511
( S T O - 3 G . C.1
' 0
19
29b
l p = l5 3 0 1
7814
t
2aU
30
H-C-N-0
Method
SCF
CH3
CI
SCF
OH
Exptl
SCF
Exothermicity,
kcal mol-
Barrier,
kcal mol-
Ref
9.5
14.6
17.3
15
60.1
40.2
34.9
60.4
38.4
38.8
61
61
62
63
This work
;&=
2
N/H
31
L-
32
, ,,QN5:p..
o=C=NYH
O=C-N
/.?, , ,I
(81
30a
I
i e = z o . +=z981
18
(4-31GJ
7815
is of little consequence whether it is in fact a saddle point which
connects the cyanic acid and formylnitrene regions and hence
a transition state on path B, or rather the transition state for
the expulsion of an oxygen atom from HOCN, and we have not
investigated this problem in greater detail. In either case the
theoretical results suggest that cyanic acid is more stable
towards intramolecular rearrangement than is the experimentally characterized molecule formonitrile oxide and thus
should be observable under nonionizing condition^.^^,^^
The Existence of Cyclic CHNO Isomers. At various points
in the preceding discussion we have mentioned reaction paths
leading from cyclic to open-chain C H N O isomers. Since one
of these species, oxazirine (7), has been invoked as an intermediate in chemical reaction^,^^ we find it appropriate to review our results for the cyclic isomers in a more concise
form.
Isomer 9, which may alternatively be viewed as an oxygen-protonated oxazirinyl anion or a complex of O H and C N ,
is unstable at the 4-31G level, and not a true intermediate. In
fact, our calculations suggest that it is rather close to the
transition state for the carboxime-cyanic acid rearrangement.
On the other hand, our extended basis set calculations do
predict the existence of an oxaziridinylidene molecule (10).
We estimate that this species is 131 kcal mol-' less stable than
isocyanic acid. Our theoretical data suggest that oxaziridinylidene could collapse virtually without activation (the
overall barrier is only 2 kcal mol-') to carboxime or to H N C
0.
The third potentially stable cyclic C H N O isomer is oxazirine (7). Our most reliable results indicate that oxazirine is
not a stable molecule. Attempts to synthesize this species will
most likely result in the formation of isocyanic acid.
Galactochemical Speculations. On the basis of our calculations, we have predicted that both cyanic acid ( H O C N ) and
carboxime (HONC) should be quite stable with respect to
intramolecular rearrangement. Failure to observe these molecules to date may well be due to complicating intermolecular
reactions. It is of interest that the related molecule, hydrogen
isocyanide (HNC), which has likewise been predicted6' to be
stable toward intramolecular rearrangement but which for a
long time had eluded experimental observation, has recently
been detected in the l a b ~ r a t o r y . ' ~
A major impetus for the experimental studies on H N C has
been the conjecture that this molecule might exist in the galactic sources W51 and DR21.73In these circumstances, individual molecules are widely separated and intermolecular
side reactions are not a problem. Such conditions are similarly
likely to enhance the probability of detection of our cyanic acid
and carboxime molecules. We note that isocyanic acid has
already been detected in the galactic center source Sgr B2.74
It is tempting to speculate that the other stable C H N O isomers
may also be observable in interstellar space.
activation energy toward intramolecular rearrangement. It should therefore be observable under appropriate conditions. Such conditions exist in the interstellar medium.
Carboxime is a somewhat higher energy isomer of
C H N O . However, the barrier to intramolecular rearrangement is sufficiently high that this species should
also be observable under appropriate conditions.
The rearrangement of formonitrile oxide to isocyanic
acid does not proceed via metastable intermediates.
However, a minimum energy path may be drawn which
involves geometries resembling oxazirine and formylnitrene.
Singlet formylnitrene is predicted to collapse without
activation to isocyanic acid.
The cyclic C H N O isomers correspond to very shallow
minima or no minima at all. Our results suggest that
none of the cyclic species is stable enough to be observa ble.
We are aware of the possible pitfalls in using single determinant molecular orbital theory to calculate entire potential
energy surfaces. We believe nevertheless that our study has
provided the overview of the C H N O potential surface that will
facilitate the application of more sophisticated theoretical
procedures. Although we do not expect that our more important qualitative conclusions will have to be revised, we regard
the more refined calculations as ne~essary,'~and we have
stated where additional theoretical work would be of greatest
interest. We note that to carry out a study of the full C H N O
surface at the double { polarization correlation level in a
detail comparable to that of the present work would be an
immense computational task and well beyond our current
computational resources. Many of our predictions can be
checked experimentally and await verification. We hope that
further experimental work will be forthcoming and we expect
that such work will demonstrate that theoretical chemistry has
reached the state of a useful predictive tool.
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(43)The only CHNO isomer which is not contained in our contour surfaces is
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(44)The contour plots were generated on the Siemens 4004 at Regensburg
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(75)After this manuscript was completed, we became aware of an independent
theoretical study of the four CHNO isomers 1-4 by A. D. McLean and coworkers at IBM (San Jose). Their calculations have been carried out at a
higher level of sophistication than have ours but the conclusions are in
substantial agreement with those reported herein. We are indebted to Dr.
McLean for bringing this work to our attention.