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Microwave Spectrum, Structure, Dipole Moment and

Centrifugal Distortion of Nitrosomethane
Dipole Moment of Acetaldehyde
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BY PAUL H. TURNER? AND A. PETER COX*

Department of Physical Chemistry, University of Bristol,
Cantock's Close, Bristol BS8 1TS

Received 15th July, 1977

The microwave spectra of ten isotopic species of nitrosomethane have been measured enabling
structures for CH3N0 and CD3N0 to be determined independently. The mean of these structures
is found to be : N=O = 1.211, C-N = 1.480, C-Hi (in plane) = 1.094, C-Ho (out-of-plane) =
1.094& LCNO = 113.2, LHiCN = 111.0, LHoCN = 107.2 and LHoCHo = 109.2'. The
methyl group is tilted by 2.5"away from the oxygen atom. The orientation of the dipole moment in
nitrosomethane has been determined from isotopic measurements. For CH315N0, higher order
Stark perturbation terms, arising through an accidental near degeneracy, had to be included to
obtain an accurate dipole moment. The components of the dipole moment are; pu = 2.262,
pb = 0.516 and p = 2.320f0.004 D. The orientation of the dipole moment in the related molecule
acetaldehyde has been determined from isotopic work and previous Stark effect measurements have
been refined to give pa = 2.537, pb = 1.062 and p = 2.750k0.006 D.
A, E splittings in the microwave spectra of CH3N0 and CD3N0 have been analysed by both
the principal axis method (PAM) and the internal axis method (IAM) for a rigid top-rigid frame
model. An attempt to fit the spectrum of CD3N0 was made using Woods' IAM treatment in
conjunction with Watson's centrifugal distortion theory. More precise distortion constants were
then obtained from the spectra of sym-CH2DN0 and sym-CHD2N0 and used to determine a
preliminary harmonic force field for nitrosomethane. A few perturbations in the spectra of the
symmetric species have been observed due to sym-asym interactions. The structure, bonding and
vibrational properties of nitrosomethane are discussed.

INTRODUCTION
The microwave spectrum of nitrosomethane was previously obtained by Coffey,
Britt and Boggs by dosing from a sample of the trans dimer at room temperature.
They reported rotational constants for CH3N0 and CD,NO, the barrier to hindered
rotation of the methyl group, the electric dipole moment and quadrupole coupling
constants at nitrogen. They also established the methyl group conformation as
eclipsing the nitrosyl bond, but had insufficient data for an accurate structure deter-
mination. Liittke attempted to record the infrared spectrum of nitrosomethane
monomer by dissociating the dimer in a heated gas cell but found difficulty due to
rapid tautomerisation. Recently, an infrared assignment of the monomer in an
argon matrix at 20 K has been r e p ~ r t e d . ~Dixon and Kroto had earlier observed
the electronic spectrum of the monomer by flash photolysis of tertiary butyl nitrite.
In the present paper a precise structure for nitrosomethane is given, based on the
microwave spectra of ten isotopic species. The structures of several other small
nitroso compounds have previously been determined by studies in this laboratory,
t Present address : Department of Chemistry, Harvard University, Cambridge, Massachusetts
02138, U.S.A.
533
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534 MICROWAVE SPECTRUM O F NITROSOMETHANE

in particular cis and trans nitrous acidsY6dinitrogen trioxide and trifluoronitroso-

methane.8 The chemical bonding in nitrosomethane will be discussed in relation to
these data. Further structural interest in nitrosomethane stems from the barrier
to internal rotation for which molecular orbital calculations have already been
performed. * O Sizeable centrifugal distortion shifts are also measurable in the
microwave spectrum of nitrosomethane, providing valuable information towards
determination of the molecular force field. However, a centrifugal distortion analysis
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is complicated by the large A , E splittings of rotational transitions due to tunnelling

of the methyl group. It will be shown that precise centrifugal distortion constants,
relatively free from barrier effects, can be obtained from the spectra of the partially
deuterated species as previously demonstrated for acetaldehyde. A centrifugal
distortion treatment for nitrosomethane, giving accurate frequency predictions for
transitions outside the observable microwave region, is also necessary for radio-
astronomy work on this molecule. Attempts to detect nitrosyl compounds in
interstellar space, including nitric oxide itself, have so far been unsuccessful.
Charge properties of nitrosomethane (dipole moment with orientation, and
quadrupole coupling constants) have also been thoroughly investigated in the present
work. In addition the dipole moment orientation in the iso-electronic molecule
acetaldehyde has been determined.

EXPERIMENTAL
The microwave spectra of all nitrosomethane species were studied using a conventional
klystron operated 100 kHz Stark modulation spectrometer with a 3 m stainless steel X-band
cell cooled with dry ice. Nitrosomethane monomer was dosed into the microwave cell
using the following procedure on the vacuum line of the spectrometer. A sample of white
dimer was gently heated and blue monomer, formed by dissociation of the dimer, was
condensed at liquid nitrogen temperature. On allowing the condensate to warm up, the
monomer either dimerised or evaporated into the cell. Initial monomer pressures of about
1-5 N m-' were used, the lower pressures being necessary to resolve some of the quadrupole
fine structure. A spectroscopic dose lasted several hours in the cell but the pressure slowly
decreased due to dimerisation on the cell walls.
Preparation of CH3N0, CHJ1'NO and CH3N180 dimers and the corresponding tri-
deuterated dimers depended on the following convenient method for preparing tertiary
butyl nitrite
4NO+02 4 2N203 (11
+
N203 2(CH3)3COH 4 2(CH3)3CONO H20. + (2)
Subsequent photolysis of the tertiary ester gave the trans-nitrosomethane dimer.2*l 2 For
CH3N0 dimer, nitric oxide was mixed with oxygen in the molar ratio 4 : 1. The dinitrogen
trioxide formed was then allowed to react with tertiary butanol below 0°C. In the absence
of excess alcohol, the yellow ester floated as an oily liquid on top of the aqueous Iayer even
at dry ice temperature and could be easily separated by low temperature vacuum distillation.
By further distillation at - 120"C, the more volatile impurities of oxides of nitrogen could
be removed from the ester. This last purification step was important for the photolysis
stage. The presence of excess alcohol, or even water, did not diminish nitrosomethane
production. Approximately mol of the ester was prepared. Photolysis of the ester
in an evacuated silica tube for three hours gave nitrosomethane dimer crystals, as described
in ref. (12), and acetone, which could be removed by pumping at room temperature.
A 30 % enriched sample of CH3N180 dimer was prepared in a similar way using
93 atom % l 8 O2 gas. For CH3lSNO dimer, the nitrogen-15 source was 7 mol dm-3
Hl5NO3 (95 % enriched). This was converted into 15N0 by the Lunge reaction l 3 of
nitric acid on mercury in excess sulphuric acid. Similarly enriched samples of CD3N0,
CD315N0 and CD3N180 dimers were prepared from tertiary [2Hlo]butanol (99 atom %,
Aldrich Chem.).
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P. H. T U R N E R A N D A . P. C O X 53 5
A mixture of partially deuterated nitrosomethane dimers was prepared by the following
reaction sequence ; (i) acetone was allowed to exchangewith D 2 0in the presence of K z C O ~ , ' ~
(ii) the partially deuterated acetone was reduced to isopropanol with sodium borohydride,
(iii) the partially deuterated isopropanol was esterified with N203,followed by photolysis
of the partially deuterated isopropyl nitrite. A dimer sample which mainly gave the spectra
of CH3N0 and CH2DN0 monomers was prepared from 1 cm3 acetone, 1.2 cm3 of D2O
and 0.003 g of K2C03. A second dimer sample giving ~ 5 %0 CHDzNO and ~ 5 %0
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CD3N0 was prepared using excess D20.

Pyrolysis of a mixture of CH3N0 and CD3N0 dimers failed to produce any microwave
spectrum attributable to the partially deuterated nitrosomethanes.

MICROWAVE SPECTRA A N D A S S I G N M E N T
The microwave spectrum of nitrosomethane is characteristic of a near-prolate
asymmetric rotor (IC= -0.95). However, species with symmetric internal rotors
show A , E doubling of transitions, up to 700MHz in CH,NO and 200MHz in
CD,NO. The two approaches which have been applied to the high barrier case in
single-top molecules are the principal axis method (PAM)15*l 6 and the internal axis
method (IAM).179 Although both methods assume a rigid top-rigid frame model
they differ in the choice of reference axis systems ; this affects the kinetic energy terms
in the respective Hamiltonians. Coffey et aZ.l used an IAM treatment for nitroso-
methane and found the V3 barriers for CH,NO and CD3N0 to be 1137 and
1095 cal mol-1 respectively. In the present work, a PAM treatment has also been
adopted whereby an effective rotational Hamiltonian, H,,, for each torsional state
obtained from an nth order perturbation calculation is written as

where

and

The notation is from ref. (16) in which 1, is the direction cosine of the top axis with
the gth principal axis and F is the reduced rotational constant for the methyl torsion.
The perturbation coefficients, W k ) , decrease rapidly with increasing n and reduced
barrier height s (= 4V3/9F). If the barrier is relatively high then H,, correct to
second order is given by

where
A,, = A . +F W::)p," (5)
B,, = Bo +FWSz'pg
c,, = c,.
The C constant for nitrosomethane is unaffected by internal rotation to second order
because p c = 0 (ab plane of symmetry). A o , Bo and Co are rotational constants of
the rigid molecule. For A levels (a = 0) only terms with n even are allowed and if
the cross term is ignored the resulting Hamiltonian will represent a pseudo-rigid
rotor with rotational constants, A,, etc., slightly altered by the internal rotation.
For E levels ( 0 = + I ) all W k ) are non-vanishing and the E levels can deviate
considerably from a rigid rotor particularly when the linear terms in Pg are not small
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536 M I C R O W A V E S P E C T R U M OF NITROSOMETHANE

compared with the separation of asymmetric doublet states which they connect. The
selection rules are those of a normal rigid rotor plus the restriction, ACJ= 0. There-
fore, in this approximation the A-state spectrum can be treated as a pseudo-rigid
rotor. Deviations of the A-state spectrum from a pseudo-rigid rotor may arise
through higher order terms in the PAM torsion-rotation Hamiltonian combined
with ordinary centrifugal distortion effects.
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TABLE a AND OBSERVED FREQUENCIES (MHz) OF CH3N0

1.-CALCULATED
transition
J’-J F’-F %?bS .%., Avd $i
l,

21 707.31 21 707.31 0.00 21 702.46

3-2 16 383.62 17 088.05
4-3 16 381.76 16 382.21 0.00 17 086.11
2-1 16 380.81 17 084.97
40.4-3 i,3 4-3 39 689.08
5-4 39 687.28 39 687.75 0.76
3-2 39 686.70
41,3+,4 4-4 11 981.94 12 039.20
5-5 11 978.00 11 979.04 0.00 12 035.31
3-3 11 976.97 12 034.31
5-5 17 966.10 17 959.03
6-6 17 962.12 17 963.23 0.01 17 955.06
4-4 17 961.31 17 954.26
5-6 34 408.81
6-7 34 406.52 34 407.15 - 212.55
4-5 34 406.05
6-6 25 138.80 25 078.47
7-7 25 134.75 25 135.90 0.02 25 074.48
5-5 25 134.05 25 073.72
71,6-7 1.7 7-7 33 491.04 33 380.74
8-8 33 487.05 33 488.20 0.02 33 376.70
6-6 33 486.44 33 376.11
10-1 0 10 111.05 10 346.96
11-1 1 10 110.23 - 1.32
10 109.82 10 345.76
9-9
11-11 14 345.41 14 511.81
12-12 14 344.42 - 3.66
14.342.92 14 510.33
10-10
122,10-122,11 12-12 19 647.45 19 771.18
13-1 3 19 646.40 -7.88
19 645.87 19 769.49
11-11
13-1 3 26 103.38 26 198.97
14-14 26 102.11 - 14.65
26 101.49 26 197.08
12-12
14-14 33 772.33 33 849.26
15-1 5 33 772.33 -25.17
33 771.56 33 847.15
13-13
a Calculated frequenciesfrom constants of table 13 (CH3N0species) or table 14 (CD3N0species) ;
b accurate to f0.05 MHz ; C hypothetical centres obtained using coupling constants from ref. (1) ;
d AV = v& - V& ; e observed frequencies taken from ref. (1).
 View Article Online

P . H. T U R N E R A N D A . P . C O X 537
In the present work a few a- and b-type transitions, in addition to those of ref. (l),
have been measured for CH3N0 (see table 1). The frequency measurements of
ref. (1) for CH3N0 and CD3N0 are in excellent agreement with this work with one
exception. The lo,l-Oo,oA- and E-state lines of CH,NO have been remeasured to
be 21 707.31 MHz and 21 702.46 MHz respectively, a correction of over 5 MHz.
The previously measured A , E doublet splitting is correct. Hypothetical centres of
the quadrupole structure for the transitions in CH,NQ have been calculated using
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the previously determined quadrupole coupling Constants (xaa = 0.5, x b b = -6.016

and xcc = 5.518 MHz) and the first order perturbation expression of Bragg and
Golden.lg The A-state spectrum of CH3N0 has been fitted using an effective rigid
rotor Hamiltonian apart from the Q-branch, = 1 p a lines which have been
analysed for B- C + 8R5 and dJ using the first order centrifugal distortion theory of
Kivelson and Wilson.20 In this case, however, dJ also contains possible fourth order
terms from the PAM torsion-rotation Hami1tonian.l Neglecting R5,this value of
B - C was combined with the lo,l-Oo,o transition to give B and C rotational constants.
An A rotational constant was derived from the b-type, 30.3-21,~transition. Again,
this constant may contain a small contribution from centrifugal distortion (up to
3 MHz). The observed and calculated spectra of CH3N0 are given in table 1 and
the spectroscopic constants are given in table 13.
The previous measurements of CD,NO have been considerably extended in the
present work since this species, with smaller A, E splittings, was found to be more
suitable than CH,NO for a centrifugal distortion study. Identification of high J lines
in CD,NO was mainly through spectral fitting, characteristic quadrupole splitting
and radio frequency-microwave double resonance 21 in cases where there was a
pumpable, pa Q-branch connection. The measured frequencies of CD,NO (see
table 2) have been corrected for quadrupole fine structure using the coupling constants
of ref. (1). The fit to the A-state spectrum of CD,NO, also given in table 2, is from
a rigid rotor treatment analogous to CH3N0 and provides a uniform set of rotational
constants suitable for structural purposes. A different treatment is required for
higher J and K l lines, which show appreciable centrifugal distortion shifts and
internal rotation splittings, and they have been excluded from the fit (see section 6).

TABLE 2.t-cALCULATED a AND OBSERVED FREQUENCIES (MHZ) OF CD3NO

All tables have been deposited with the British Library Lending Division, Supple-
mentary Publication Number SUP 22197 (46 pp.).f This table contains 47
transitions (A and E) with quadrupole fine structure comprising 1 4 9 microwave
frequencies. See table 1 9 for some of the A / E splittings and table 2 1 for hypo-
thetical centres of A-state lines.
t See footnotes to table 1.
$ See Notice to Authors in J.C.S. Faraday, 1976, Index issue.

TABLE
3. -/'-CALCULATED AND OBSERVED FREQUENCIES (MHZ) OF CH3 5 N 0
transition
J'-J Avd

~O,l-OO,O 2 1 649.34 0.00 2 1 644.79

3 0,3-2 1,2 1 8 085.98 0.00
5 1.4-5 1,s 1 8 745.65 0.01 1 8 729.28
52,3-61,6 30 0 2 5 . 8 1 - 178.03
61.5-61,6 26 2 2 9 . 0 4 0.01 26 1 6 6 . 2 3
132, I 1-1 32,12 29 026.65 -15.53 29 1 0 6 . 1 3
t See footnotes to table 1.
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538 M I C R O W A V E SPECTRUM O F NITROSOMETHANE

TABLE
4.T-cALCULATED a AND OBSERVED FREQUENCIES (MHZ) OF CH3N1'0
transition
J'-J Ff-F 4. d.c Avd Vfbbe I ,

~O,l-OO,O 20 709.82 20 709.82 0.00 20 705.40

21,241.1 1-1 40 305.20
3-2
40 302.48
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2-1 40 302.37 - 1.98

1-0
40 300.76
2-2
3-2 13 638.69
4-3 13 636.79 13 637.24 -0.54
2-1 13 635.83
4-3 35 847.46
5-4 35 845.63 35 846.10 0.00;
3-2 35 845.03
5-5 16 723.68 16 718.75
6-6 16 719.70 16 720.80 -0.02 16 714.71
4-4 16 718.88 16 713.95
6-6 23 401.59 23 348.40
7-7 23 397.50 23 398.69 0.01 23 344.32
5-5 23 396.87 23 343.66
7-7 31 179.36 31 081.08
8-8 31 175.28 31 176.47 -0.01 31 077.00
6-6 31 174.70 31 076.42
8-8 40 045.71 39 902.13
9-9 40 041.61 40 042.84 0.00 39 897.95
7-7 40 041.13 39 897.50
14-14 29 890.37 29 954.78
15-1 5 29 889.08 -24.40
29 888.43 29 952.85
13-1 3
15-1 5 37 891.50 37 938.22
16-16 37 890.04 - 38.21
37 889.28 37 936.14
14-14
t See footnotes to table 1 .
The spectral assignment of the nitrogen-I 5 , oxygen-I 8 and carbon-13 species of
CH3N0 and CD3N0 is given in tables 3-8, and the spectroscopic constants for the
A-state spectra are given in tables 13 and 14. Rotational constants for CH315N0,
CH3N180 and CD3N180 were derived as for the main species. For CD315N0,
only one Q-branch, K l = 1 transition was measured and so JJ for this species was
assumed the same as for CD3N0. The carbon-13 species of C H 3 N 0 and CD3N0
were measured in natural abundance. For 3CH,N0, assignment of Q-branch
Kl = 1 lines was made difficult by interference from main species lines ; fortunately
the 71,6-71,7 A-state and 61,5-61,6 E-state lines could be measured. An accurate
B - C was derived from the 71,6-71,7 transition assuming 6J from the main species.
Due to the weakness of the b-type spectrum, the A constant for 13CH3N0had to be
derived from the po @branch K l = 2 series. Use of A, E splittings and quadrupole
structure was particularly important for definitive assignment of these lines. Transfer
of distortion shifts from the main species gave the A constant for 13CH3N0to within
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P. H . T U R N E R A N D A . P. C O X 539
1 MHz. The A rotational constant for 13CD3N0 was obtained by a similar
procedure.

5.t-cALCULATED
TABLE * AND OBSERVED FREQUENCIES (MHZ)OF ’3CH3N0
transition
F’-F ebs Vf.C Av

21 073.38 21 073.38 0.00 21 068.80

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6-6 23 791.72
7-7 obscured 23 787.67
5-5 23 787.04
7-7 31 763.75
8-8 31 759.75 31 760.90 -0.04
6-6 31 759.13
13-1 3 23 664.70
14-14 23 663.51 - 15.03
23 662.91
12-12
14-14 30 687.90 obscured
15-1 5 30 686.57 -25.05
30 685.89 30 773.03
13-1 3
15-1 5 weak 38 957.25
16-1 6 38 887.27 -36.92
38 886.53 38 955.06
14-14
t See footnotes to table 1.
TABLE6.t-CALCULATED a AND OBSERVED FREQUENCIES (MHZ) OF CD3’ 5 N 0
This table (containing data comparable with table 3) has been deposited with the
British Library Lending Division.
-t See footnotes to table 1.
TABLE7.t-cALCULATED a AND OBSERVED FREQUENCIES (MHZ) OF CD3N’ ‘0
This table, containing data comparable with table 4, has been deposited with the
British Library Lending Division.
1- See footnotes to table 1.

TABLECALCULATED a AND OBSERVED FREQUENCIES (MHz) OF 3CD3N0

This table, containing data comparable with table 5, has been deposited with the
British Library Lending Division.
1- See footnotes to table 1.
TABLECA CALCULATED AND OBSERVED FREQUENCIES (MHz) OF SYM-CH~DNO
J’J F’-F vobs a vh.c vh.c-Vcalc

This table has been deposited with the British Library Lending Division. It
contains 36 transitions with 66 measured quadrupole components. See table 23
for hypothetical centre frequencies.
Accurate to 0.05 MHz ; b hypothetical centres obtained using coupling constants of ref. (1) ;
C calculated frequencies from centrifugal distortion treatment.
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540 MICROWAVE SPECTRUM OF NITROSOMETHANE

TABLE10.j--CALCULATED AND OBSERVED FREQUENCIES (MHZ) OF SYM-CHDZNO

This table has been deposited with the British Library Lending Division. It
contains 42 transitions with 72 measured quadrupole components. See table 24
for hypothetical centre frequencies.
7 See footnotes to table 9.
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TABLE11.t-OBSERVED FREQUENCIES (MHZ)b OF ASYM-CH2DNO AND ASYM-CHD2NO

asym-CHzDNO asym-CHDZNO
transition Vcbs Vcbs

lo,l-Oo,o 20 220.32 19 538.12

20 218.55 19 537.07
7 See footnotes to table 1.
The microwave spectra of the partially deuterated nitrosomethanes have been
investigated in considerable detail (see tables 9, 10 and 11). In addition to the
determination of the methyl group structure, these species are important for centrifugal
distortion purposes.1 The 1o, l-Oo,o transitions in sym-CH,DNO, sym-CHD,NO
and the corresponding asymmetric forms were located to 5 MHz in ref. (1) in order
to determine the methyl group conformation. In the present work, these transitions
were accurately measured as singlets in the symmetric species and as doublets in the
asymmetric forms (due to tunnelling between two equivalent potential minima).
For sym-CH,DNO and sym-CHD,NO, the strong a-type, K-l = 1 and K-l = 2
series were easily identified enabling determination of the B and C rotational constants.
Low J, b-type lines were then predicted on the basis of an A constant derived from
the inertial defect relationship,
A f = I c - r a - I b = A-2C.mi<ci>2 (6)
TABLE12.t-oBSERVED FREQUENCIES (MHZ)b FOR U = 1 TORSIONAL STATE FOR NITROSO-
METHANE SPECIES
transition
species J'-J F'-F 4 x 4 d.0 .fbS

CH3NO 10,1-00,0 21 633.40 21 633.40 21 706.39

CH3N180 10,1-00,0 20 713.43
CD3NO 10,1-00,0 18 412.77 18 412.77 18 449.13
20,2-10.1 36 810.90 36 810.90 36 883.90
21,241.1 1-1 36 071.52

2-1
3-2
l-O 1
1 36 068.83
36 068.71

36 067.17
2-2 I 37 641.32

2-1 1 37 639.64 37 639.64

37 637.05
17 573.25 17 573.25
36 699.27 36 699.27
t See footnotes to table 1.
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TABLE
13.-ROTATIONAL CONSTANTS (MHZ), MOMENTS OF INERTIA AND INERTIAL DEFECTS (a.m.U.A") OF CHJNO ISOTOPIC SPECIES
CH3NO CH p N O C H ~ N ~ ~ O 13CH3NO sym-CHZDNO

A 61 284.01 50.05 59 441.88 5 0.05 60 426.425 0.05 61 054.3 51.0 51 434.67k0.14

B 11 452.77 k0.03 11 449.91 k0.03 10 912.56k0.03 11 104.83+_0.03 11 158.4750.03
C 10 254.54 k0.03 10 199.43k0.03 9 797.26k0.03 9 968.55f0.03 9 728.8250.03
x
~ J 103 1.972+0.003 1.8550.01 1.75k0.01 (1.972) 1.83k0.04
la 8.246 46f0.000 01 8.502 0250.000 01 5.363 49+0.000 01 8.277 5 *O.OOO 1 9.825 59+0.000 03 y
Ib 44.127 0 +O.OOO 1 44.138 0 +O.OOO 1 46.311 4 &O.OOO 1 45.509 6 +O.OOO 1 45.2908 +O.OOO 1
Ic 49.283 1 +O.OOO 1 49.549 4 +o.ooo 1 51.583 4 &O.OOO 1 50.697 0 +O.OOO 1 51.946 3 +O.OOO 2 *
Ic-Ia-Ib - 3.090 4 50.000 1 - 3.090 6 k0.000 1 - 3.091 5 50.000 1 - 3.090 1 +_O.OOO 2 -3.170 1 +_0.0002
w
a Rotational constants for Atorsional state except for the sym-species ; b constants from centrifugal distortion fit (errors quoted 1m) ; c errors for A state 1:
constants reflect experimental uncertainties and not model errors. E
>
Z
TABLE
14.t-ROTATIONAL CONSTANTS " (MHZ), MOMENTS OF INERTIA AND INERTIAL DEFECTS (a.m.U. A') OF CDsNO ISOTOPIC SPECIES '*
CD 3NO CD 315NO CD3N1*0 13CD3N0 sym-CHDzNO
?
A 44 010.51 k0.05 42 995.665 0.05 43 570.11k0.05 43 941.6 51.0 51 006.40+0.14 0
B 9 639.42k 0.03 9 630.855 0.03 9 187.83f0.03 9 427.99+ 0.03 9 816.38k0.03 0
C 8 776.45_+ 0.03 8 728.17+0.03 8 384.4220.03 8 597.95k 0.03 9 182.89k0.03
x
~ J 103 1.17+ 0.01 (1.17) 1.0550.01 (1.17) 0.69k0.02
la 11.483 OS_+O.O00 01 11.754 12+0.000 01 11.599 1550.000 01 11.501 1 +O.OOO 3 9.908 09+0.000 03
Ib 52.428 1 +0.000 2 52.474 7 +O.OOO 2 55.004 9 _+O.OOO 2 53.603 8 +0.0002 51.483 0 f0.000 2
Ic 57.583 2 +O.OOO 2 57.901 7 kO.000 2 60.275 6 50.000 2 58.778 7 _+0.0002 55.034 5 fO.000 2
Ic-la-Ib -6.328 0 f 0.0003 -6.327 1 _+ 0.000 3 - 6.328 5 _+0.0003 - 6.326 2 _+0.000 3 -6.356 6 f0.000 3
j- See table 13 for footnotes.
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542 M I C R O W A V E SPECTRUM OF NITROSOMETHANE

by transferring the experimental values of A' from the closely analogous partially
deuterated acetaldehydes. These transitions were then assigned through spectral
position and quadrupole pattern. High J lines in both sym-CH,DNO and sym-
CHD,NO were assigned mainly through spectral fitting. The (observed minus
calculated) columns of tables 9 and 10 represent the deviations of the measured lines
for sym-CH,DNO and sym-CHD,NO from a centrifugal distortion treatment (see
section 6) with the rotational constants given in tables 13 and 14.
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Table 12 contains some measured transitions in the zt = 1 torsionally excited state

for nitrosomethane species. The intensities of these satellite lines, lying close to the
ground state transitions, at dry ice are about one third of the mean species in rough
agreement with a torsional fundamental frequency of 146 cm-l estimated from the
V3 barrier. As expected, the lo,l-Oo,o torsional satellites show large A , E splittings
in good agreement with predictions based on the V3 barrier determined from the
ground state spectrum.

DIPOLE MOMENT AND STARK EFFECT

The dipole moment of nitrosomethane was reinvestigated to determine the
orientation of the dipole in the molecule. The nitrogen-15 sample was chosen to
enable the dipole moment to be obtained free from Stark-quadrupole interaction.
However, the effects of internal rotation (e.g., on energy level differences) had to be
carefully considered in order to obtain a valid dipole moment. It, therefore, seemed
appropriate to refine the dipole moment measurements of acetaldehyde, with
similar internal rotation, and at the same time establish the dipole orientation in
that molecule as well.

(i) N I T R O s o M E T H A N E
For the purposes of the Stark effect, the A-state spectrum of nitrosomethane can
be treated as an effective rigid rotor. However, as has already been shown in the
rigid rotor A-state fits for nitrosomethane, this approximation fails for energy levels
with K l2 2 (see, for example the fit to the 52,3-61,6 transitions in C H 3 N 0 and
CH315N0in tables 1 and 3, respectively). For E levels, the linear term in P,which
can contribute a first order Stark effect, is significant for all but the K = 0 energy
levels. Also, the effect of ignoiing the cross term (PgPgp+PgtPg) in the second order
PAM Hamiltonian (4) is to rotate the effective principal axis system of the A state
from the principal axes of the molecule with frozen internal rotation by the angle 4
such that l 5
tan 2$ = 2Fp,p, W$:L o/(A-B). (7)
This changes the definition of the dipole components along the principal axes, but
for CH315N04 is negligibly small (-3').
All the Stark measurements were made at dry ice temperature using X-band
waveguide. The d.c. bias method was used with positive polarity relative to the
superimposed 200 V square wave modulation. The cell was calibrated against the
M = 0 and M = 1 lobes of the J 1 -+ 2 transition of OCS for which the dipole
moment was taken to be 0.714 99 D.22 Polarisability and a small fourth order
contribution (0.19 MHz for M = 0 at 3.9 kV cm-l) to the Stark effect 23 was taken
into account in the calibration procedure.
Investigation of the M = 0, lo,l-Oo,oA-state transition of CH315N0 gave an
accurate determination of pa. The E lobe was found to have the same Stark coefficient
and therefore pa to be the same for both A and E states. ,ub for CH,15N0
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P. H. TURNER A N D A . P. COX 543

was determined from Stark effect measurements on the M = 4 and M = 2
components of the 61,5*-61,6A-state transition. The strong p b dependence of this
transition is caused by an accidental near-degeneracy with the J = 5, K l = 2
asymmetry doublet (see fig. 1). The allowed dipole moment connections for
the second order Stark perturbation energy are indicated in fig. 1 by solid arrowed
lines with a or b representing the active component of the dipole. The small
energy difference between the 52,4 and 61,5 levels in CH315N0 is seriously in error
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(-200 MHz) using the rigid-rotor Hamiltonian for the A-state. This energy
difference has, therefore, been calculated from the measured 52,3-61,6 and 61,5-61,6
transitions and the calculatedJ = 5, K1 = 2 asymmetry splitting. The second order
Stark coefficients for the 61,5-61,6 transition in CH315N0, obtained from the effective
A-state rotational constants, were then corrected for this accidentally close interaction
using the method of Golden and Wilson.24 The M = 2 and M = 4 lobe displace-

GHz

0.8

2.9

26-2

(i) (ii)
FIG.1.-Stark perturbation (2nd and 4th order) on the 61,5(i) and 61,6 (ii) levels of CH3I5NO.

ments were measured for various d.c. voltages between 1 and 2 kV and graphs of Av
against Y 2 were plotted (see fig. 2). It is apparent.that attempts to draw straight
lines through the M = 4 and A4 = 2 plots give unacceptably large errors for the
zero-field intercept. There is a definite curvature for both components, especially
noticeable for M = 4, arising through neglect of higher order perturbation terms in
the Stark energy. For an asymmetric rotor all odd perturbation terms are zero
and the displacement of a particular Stark component is given simply as,24
Av = ap2E2+bp4E4+cp6E6+. . .. (8)
To test for fourth order perturbation terms, graphs of Av/V2 against V 2 were plotted.
If only fourth order effects are present a straight line would be expected from eqn (8).
However, this technique is sensitive to the observed value of the zero-field line, v,,,
which could cause a slight curvature to the graph. A curvature is in fact
particularly for the M = 4 plot and cannot be accounted for by an error in y o .
Therefore, fourth order contributions are present but further, sixth order perturbation
terms exist which made it difficult to determine A v / V 2 graphically. It was, therefore,
necessary to calculate the fourth order contribution to the Stark effect of the 61,5-61,6
transition in CH315N0.
Fourth order Stark perturbations have previously been observed in the near oblate-
top molecule, pyrazo1e.26 In pyrazole, the small asymmetry doublets would be
connected by the pc component of the dipole which is, however, zero being perpen-
dicular to the molecular plane. Thus no effect of these near degeneracies is seen in
11-1 8
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544 M I C R O W A V E S P E C T R U M OF N I T R O S O M E T H A N E
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(voltage)2/kV2
FIG.2.-Stark effect of 61,5-61,6 A-state transition in CH3I5NO. (a) M = 4, (b) A4 = 2 ; (-)
observed data, (- - -) quadratic plot after fourth and sixth order corrections.

second order, but they are connected in fourth order by means of a third state (or
several other states). The fourth order correction term is given by

where EA2)is the second order Stark perturbation energy, the perturbation V = -p E
and the matrix elements V,, are those of the operator Yin the unperturbed rigid-rotor
basis set. The first term in this expression for EA4) shows that n can be connected
with I even if Vn,is zero via a third level rn for which Vnmand V,, are non-vanishing.
The fourth order effect is particularly large if the denominator EA0)-E$O) is small.
Applying this theory to the situation in CH315N0[see fig. l(i)] it is now apparent
that the 6 1 . 5 level is perturbed in fourth order by a pc connection with the 52,3 level
via two pairs of a and b-type connections. Because of the larger energy differences
involved, fourth order perturbations on the 61,6 level are expected to be smaller
[see fig. l(ii)]. The direction cosine matrix elements in the asymmetric rotor basis
needed in the fourth order perturbation expression were evaluated by the method
of Lide,27which is suitable for slightly asymmetric rotors. The calculated values of
the fourth order Stark coefficients for the A-state 61,5-61,6 transition in CH315N0
were found to be :
M = 2 : AvC4)/E4= - 1.042 x MHz kV-4 cm4
M = 4 : A V ( ~ ) /=E -~ 3.188 x MHz kV-4 cm4.
 View Article Online

P . H . T U R N E R A N D A . P . COX 545
The conversion factor 0.503 44 MHz D-I V-l cm was used in deriving these quantities
together with approximate values of the dipole components. As expected, the fourth
order correction is larger for the M = 4 component, amounting to - 1.17 MHz at
4.36 kV cm-l in a total lobe displacement of 10 MHz. A sixth order analysis of the
data was then made empirically by correcting the observed Av for the fourth order
correction A v ( ~ ) ,and then plotting graphs of Av(corrected)/ V 2 against V4. These
graphs showed no detectable curvature 2 5 and the intercepts gave the second order
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coefficients,
M = 2 : A v ( ~ ) / E=~ -0.476f0.002 MHz kV-2 cm2
M = 4 : A v ( ~ ) / E=~0.615+0.001 MHz kV-2 cm2.
The slopes gave the sixth order coefficients, from which the sixth order displacements
can be shown to amount to -0.13 and -0.44 MHz for M = 2 and M = 4 at
4.36 kV cm-l respectively.
The observed second order Stark coefficient for the M = 0 component of the
lo,l-Oo,o transition was then combined with the second order coefficients from the
M = 2 and itf = 4 components of the 61,5-61,6 transition to give pa = 2.262+
0.004, = 0.516+0.002 and ,ut = 2.320+0.004 D for CH3"N0 (see table 15).
TABLE
15.-sTARK COEFFICIENTS AND DIPOLE MOMENTS FOR ISOTOPIC SPECIES OF NITROSO-
METHANE

Av E-Z/MHz kV-2 cm2

transition M observed calculated

1O , l - o O , O 0 32.13 f0.05 32.12

61.5-61.6 2 -0.476+ 0.002 -0.478
4 0.615f0.001 0.615
Pa 2.262+ 0.004 D
pb 0.516f0.002 D
Pt 2.320+0.004 D
t a r 1 (,!&/pa) 12.85 +0.07"

sym-CH,DNO
Av E-ZIMHz kV-2 cm2
transition M observed calculated
orientation (i) orientation (ii)

61,5-61,6 4 1.00 fO.01 1.04 1.21

5 1.513f0.003 1.519 1.690
6 2.115f0.005 2.106 2.272
UExperimental Stark coefficients Av for A state lo,l-Oo,o, M = 0 lobes of CH3N0 and
CH3N180are 32.03 MHz k V 2 cm2 and 33.43 MHz k V 2 cm2 respectively, thus confirming pu and
dipole orientation. b Stark coefficients measured for high field case above, -3.0 kV cm-l, see text.

Two possibilities exist for the orientation of the dipole moment relative to the
molecular framework (i) pt inclined at 52.0" to the N=O bond or (ii) pt inclined at
26.3" to the N-0 bond. Case (i) was shown to be the correct orientation by Stark
effect measurements on the M = 4, 5 and 6 components of the 61,561.6 transition

-
in sym-CH,DNO (see table 15 and fig. 3). These measurements were carried out in
the high field case above 3.0 kV cm-I. The doublet splitting of Stark components
was calculated from Stark-quadrupole theory to be 3.45 MHz for M = 6, 1.72 MHz
for M = 5 and 0.32 MHz (unresolved) for M = 4 in accordance with experimental
measurements. Fourth order Stark perturbations on the 61,5-61, transition of
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546 MICROWAVE S P E C T R U M O F NITROSOMETHANE

sym-CH,DNO were calculated to be negligible because of the larger energy spacing

of the 52.4 and 61,5levels.

(ii) A c ETA L D E H Y D E
Stark effects in the A torsional state spectrum of acetaldehyde were studied using
the effective rotational constants determined by Kilb, Lin and Wilson.15 The
strongly pu dependent M = 0, lo,l-Oo,o transition and the p,-dependent M = 0 and
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M = 1 components of the 40,4-31,3transition were selected for study. The latter

transition was chosen in preference to a pa Q-branch, K l = 1 transition to avoid
any close interactions with Kdl = 2 levels [for which the PAM Hamiltonian eqn (4)
breaks down]. The least squares slopes (Av/E2) gave the following dipole com-
ponents ; pu = 2.537+0.004 D, pub= 1.062f0.005 D and p r = 2.750+0.006 D (see
table 16).
TABLE
1 6.-STARK COEFFICIENTS AND DIPOLE MOMENTS FOR ISOTOPIC SPECIES OF ACETALDEHYDE

CH3CHO
Av E-Z/MHz kV-2 cm2
transition M observed calculated

~O,l-OO,O 0 45.92 f0.07 45.92

40,4-31,3 0 0.835+0.003 0.826
1 2.686f 0.004 2.693
Pa 2.537f0.004 D
L(b 1.06250.005 D
Pt 2.750f0.006 D
tan-l(pb/pa) 22.712 0.13"

sym-CH,DCHO
Av E-Z/MHz kV-2 cm2
transition A4 observed

40,4-31,3 0 0.716f0.004
61,5-61,6 6 4.58 k0.02
calculated
orientation (i) orientation (ii)
,Ua 2.46 rfi0.02D 2.50 2.57
pb 1.156+0.004D 1.151 0.971
pt 2.72 20.02D 2.75 2.75

The orientation of the dipole is either at 10.1"to the C=O bond, case (i), or at
55.5" to the C=O bond, case (ii). Case (i) was shown to be the correct orientation
by measuring p, and P b in sym-CH,DCHO (see table 16 and fig. 5). The results
for sym-CH,DCHO also confirm the larger value of determined for CH3CH0 in
the present work.

MOLECULAR STRUCTURE
Structures for CH3N0 and CD3N0 were determined independently from the
data as follows. Moments of inertia of isotopic species derived from their A-state
spectra were corrected to average values, free from A, E splitting, by application of
second order PAM theory in the form of expressions (5) for the rotational constants.
For CH3N0 and CD3N0 the top angles, O,, and perturbation coefficients, ?V$
needed for this correction could be taken directly from the internal rotation analyses
(see next section). For the other isotopic species, the barrier parameters could be
 View Article Online

P . H . T U R N E R A N D A . P. COX 547
derived with sufficient accuracy from a structure close to the final one and assuming
no change of V3 on isotopic substitution. The moments of inertia derived from the
spectra of the symmetric partially deuterated species needed no correction for internal
rotation.
The a- and b-coordinates of carbon, oxygen and the in-plane hydrogen (or
deuterium) atoms and the b-coordinate of the nitrogen atom in both CH3N0 and
CD3N0 were determined using Kraitchman's equations for a planar asymmetric
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rotor,

The small a-coordinate of the nitrogen atom in both molecules was obtained from the
first moment condition, Z miai = 0. The a-coordinate of the out-of-plane hydrogen
atoms in CH3N0 was determined using Chutjian's equations for symmetric
double substitution (CH3N0+ sym-CHD,NO) in the convenient form given recently
by N y g a a ~ d , ~ ~

where Pa = (-Ia+Ib+Ic)/2, etc., and p is the reduced mass for double substitution.
The a-coordinate of the out-of-plane deuterium atoms in CD3N0 was similarly
located from the isotope pair CD3N0+ sym-CH,DNO. The small b-coordinate of
the out-of-plane hydrogen (and deuterium) atoms in CH3N0 (and CD3NO) was
adjusted to fit the cross moment condition, E miaibi = 0. The out-of-plane hydrogen

TABLE
17.-PRINCIPAL AXIS COORDINATES (A) AND STRUCTURES FOR NITROSOMETHANE
CH3NO CD 3NO
U b a b

N 0.1245t -0.5113 0.2260* - 0.5265 (0.0002)

0 1 .0653 0.2516 (0.0012) 1.1556 0.2505 (0.0019)
c - 1.1864 0.1800 (0.0021) - 1.0934 0.1415 (0.0039)
Hs, D, - 1.0582 1.2665 - 0.9799 1.2318
Ha, Da - 1.7261 - 0.1489* +
-0.8905 - 1 A271 -0.2020
t Z miai = Z miajbj = 0 used to calculate these coordinates.

E mibi = 0
E mi(a:+C:) = 43.9920 (1; = 44.1394)Z mi(a?+ c?) = 52.2141 (1; = 52.4350 a.m.u. A")
+ +
Z mj(b? c?) = 8.3218 (1: = 8.2960) C mi(b? c?) = 11 S404 ( I s = 11.5047 a.m.u. A2)
bond distances (A) and angles (deg)

C-H, = 1.0940 C-D, = 1.0962+0.002

C-Ha= 1.0920 C-Da = 1.0935fO.002
N=O= 1.2112 N=O = 1.2116+0.002
C-N= 1.4820 C-N = 1.4789+ 0.002
LCNO = 113.16 LCNO = 113.25f0.3
LHsCN = 111.08 LD,CN = 110.91k 0 . 2
LHaCN = 107.26 LHaCN = 107.07+0.2
LHaCHa = 109.27 LHaCHa = 109.04f0.2
a For mean structure see fig. 3. b Figures in parentheses are corrections applied to Kraitchman
coordinates.
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548 M I C R O W A V E S P E C T R U M O F NITROSOMETHANE

coordinate in CH3N0 was obtained using eqn (1 l), given by Laurie and Her~chbach,~'
and the CH3N0+ CD,NO data
AZc- AI,- A& = (A'- A) -4(m,(~,)~ -rnH(cH),). (1 1)
A'- A was taken to be -0.015 a.m.u. A2 as suggested in ref. (31) but a better estimate
of the out-of-plane substitution coordinate should be obtained by constraining
hydrogen and deuterium to the same position. This gave a CH value of 0.8905A
in good agreement with values of 0.8922 and 0.8901 A obtained using Chutjian's eqn
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(lob) on the isotope pairs CH3N0+ sym-CHD,NO and CD3N0 + sym-CH,DNO,

respectively.
Both sets of a-coordinates shown in table 17 give 16")-0.35 % less than Iio)which
is typical of other substitution structures. Moreover, the a-coordinate of the nitrogen
atom in CH,NO, obtained from the Xmmiai= 0 condition, shows a shortening of
0.022 A in the Kraitchman coordinate, which is in favoui-able agreement with nitrous
acid where the nitrogen atom is similarly located. For CH,NO, the carbon and
oxygen Kraitchman 6-coordinates have been reduced slightly to meet the E mibi = 0
condition (see table 17). This is contrary to the foreshortening often found for small
Kraitchman coordinates, and is probably caused by the large amplitude torsional
motion. An even further reduction of these small coordinates would be necessary
to bring I $ ) below ILo) but this latter adjustment, when carried out, makes only small
changes in the structure. The situation along the b-axis in CD3N0 is similar where
minor reductions have been made to the heavy atom 6-coordinates to fit the first
moment condition. The structures of CH3N0 and CD3N0 are given in table 17
and the errors quoted will include structures with I(:) up to 0.3 % less than 16"). A
mean structure for nitrosomethane is given in fig. 3. The structure of CD3N0
b
H

>a

FIG.3.-Structure of CH3N0.
shows a shortening of 0.003A in the central C-N bond relative to CH3N0 which
is within the errors of the structural determination. However, some shortening
(-0.001 A) is expected due to the secondary isotope effect of three deuterium atoms
as found in the carbon-halogen bond of methyl bromide and chloride on tri-
deuteration.,, The structures of CH,NO and CD3N0 show methyl group tilts
away from the oxygen atom of 2.54" and 2.56" respectively where the tilt is defined
as the angle between the C-N bond and the perpendicular from the carbon atom to
the basal plane of the methyl group pyramid.
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P . H . T U R N E R AND A . P. COX 549

I N T E R N A L ROTATION A N D C E N T R I F U G A L DISTORTION
Before a centrifugal distortion analysis can be carried out for either CH3N0 or
CD,NO, the internal rotation problem has to be treated. Hence the measured
A , E splittings for CH3N0 and CD3N0 have been analysed in this section by both
the PAM and IAM. The main interest therefore in the present work is the relative
quality of the A , E fitting by both methods for an eventual centrifugal distortion
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treatment rather than the determination of the V3 barriers themselves, which has
been discussed previously in ref. (1).
(i) The PAM Hamiltonian (3), with terms up to fourth order, was used to calculate
A , E splittings in the microwave spectra of CH3N0 and CD3N0. For this purpose,
a computer program was written which sets up the matrix of Hob for A and E levels
separately in a symmetric rotor basis using the matrix elements calculated by
Herschbach l6 for P, n = 1 to 4, and including the corrections given by H i r ~ t a . ~ ~
The input data consisted of average rotational constants Ao, Bo and Co appropriate
to the rigid rotor part H,, tabulated perturbation coefficients 3 4 and the geometric
factors pa, P b and F. The A and E energy matrices, which contain elements diagonal
and off-diagonal in K up to (KIH,,IK+4), were diagonalised by the Jacobi method
for J < 20. For CD3N0, rotational constants derived from a centrifugal distortion
analysis were used. [See section (ii) and table 221. In the case of CH3N0, Co was
assumed equal to CAY Bo was calculated to fit ( + v A + + v,) for the lo,l-Oo,oA and E
transitions and A . was adjusted to fit the measured A and E 30,3-21,2transitions.
At the same time for both molecules, the three independent variables s, 8, and I, were
fitted by an iterative non-linear least squares process to the measured A , E splittings.
Tables 18 and 19 give the observed and calculated A , E splittings for a selected range
of transitions and table 20 gives the PAM barrier parameters used in the final fits.

TABLE
18.-oBSERVED AND CALCULATED A , E SPLITTINGS (MHZ) FOR CH3NO

VA-VE (obs) a

4.85 - 0.70 - 0.71

- 704.35 0.48 0.00
- 57.31 0.14 -0.04
7.06 -0.10 - 0.02
60.28 -0.08 0.00
110.32 0.06 0.01
-235.93 -63.81 -7.89
- 166.40 -51.14 -8.52
- 123.65 -43.40 -9.83
- 95.59 -38.93 - 11.75
- 75.54 - 37.77 - 14.89
a From hypothetical centres of quadrupole split A and E transitions. b Obs. -calc. splittings
from fourth order PAM theory. C Obs. -caIc. splittings from Woods IAM theory. d Observed
splitting not included in fit.

(ii) The measured A , E splittings given in tables I8 and 19 have also been analysed
using the Woods IAM computer program.35 The fitted values for the three adjustable
barrierparameters,Ao = (3/2)Fa(?),8, and I, for CH,NO and CD3N0 aregivenin
table 20.
The V3 barriers in table 20 for CH3N0 and CD3N0 are in close agreement with
the previous values of ref. (1). The fourth order PAM fits for both molecules have
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550 MICROWAVE SPECTRUM OF NITROSOMETHANE

NITRO OBSERVED AND

TABLE CALCULATED A, E SPLITTINGS (MHZ) FOR CD3NO

YA- YE(ObS) a bobs - calc AVobs - calc

1.32 -0.15 - 0.06
107.68 -0.47 -1.10
2.52 -0.42 -0.26
-11.29 0.56 0.08
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13.91 -0.18 -0.08

119.00 -0.30 - 1.00
- 121.74 0.07 1.18
121.93 0.26 -0.80
11.16 -0.11 0.73
18.96 -0.38 0.79
-228.95 0.63
27.97 -0.10 1.39
-205.18 0.39
37.66 0.03 1.83
- 222.33 -2.13
107.02 0.08
94.71 1.22
48.28 0.29 2.32
- 92.51 0.04
- 84.37 0.26
- 75.61 0.79
- 7.22 -2.17 d -0.55
- 7.52 -2.73 -0.96
- 7.51 -3.86 - 1.56
- 7.07 -5.51 -2.45
- 6.02 -7.38 - 3.53
- 7.01 - 3.96 d
-4.83 - 5.16
t See footnotes to table 18.

TABLE
2O.f-PAM AND IAM PARAMETERS FOR NITROSOMETHANE INTERNAL ROTATION
CH3NO CD 3NO
A0 = 60918.4 f0.l MHz A0 =43 927.87k0.14 MHz
Bo = 11 449.54f0.03 MHz Bo = 9 638.08f0.04 MHz
Co = 10 254.5410.03 MHz Co = 8 776.8410.03 MHz
PAM IAM PAM IAM
s= 23.32f0.02 A0 = -2149.3 &9.9 MHz s = 34.19h0.08 A 0 = -240.8 h0.8 MHz
e, = 27.79rto.050 e, = 27.81 h0.05" e, = 2ci.24f0.060 e, = 2 5 . 5 5 f o . i ~
I , = 3.2860.01 a.m.u.Az Za = 3.2910.01 a.m.u.A2 la = 6.4730.04 a.m.u.A2 Za = 6.53h0.01 a.m.u.AZ
F = 228.4 f0.8GHz F = 149.2f1.2 GHz
V3 = 1143 f 4 cal mol-1 V3 = 1095f9 cal mol-1
j- Errors quoted represented one standard deviation.

been restricted to transitions involving K-l< 1. For a given barrier height, the
importance of higher order terms in the PAM depends upon the magnitude of the
operator 9 which for a nearly prolate asymmetric rotor is given roughly by KIm/Ia.
Therefore, the PAM is best suited to light tops attached to heavy frameworks and
for low K-l transitions. Herschbach l6 suggests the inclusion of terms up to fourth
order for KI& < 0.55. For CH,NO, 9 = 0.4K and for CD,NO, 9 = 0.56 K
and so terms higher than fourth order become important for both molecules when
K-l > 1. Herschbach l6 has also shown that the effect of fourth order PAM terms
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P . H . T U R N E R A N D A . P. C O X 55 1
for the A levels simulate ordinary P4 centrifugal distortion. However, a centrifugal
distortion treatment for the nitrosomethanes based on a direct fit of Watson’s reduced
quartic Hamiltonian 36 to the A state spectra failed because of the poor convergence
of the PAM Hamiltonian for higher K-, transitions. This procedure, with terms
up to sixth order, has been carried out on thi~acetaldehyde,~~ with smaller internal
rotation effects, and the derived Watson constants were then corrected for the
torsional contribution.
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The IAM treatment of Woods 3 5 is very successful in fitting a wide range of

measured A , E splittings in CD3N0 (see table 19). The fit has been restricted to
transitions with J < 15, K-, < 3 because the Woods method appears to break down
for transitions involving higher J and K l values. The major approximation
introduced by Woods is assuming the torsional integrals diagonal and off-diagonal
in u are 1 and 0 respectively. Even the inclusion of torsional integrals calculated
using harmonic oscillator wavefunctions [as in ref. (l)] has been shown 3 8 to have no
effect on the quality of the A , E fit. The only effect is to modify the values of the
rotational constants. Therefore a centrifugal distortion analysis for CD3N0 has
been carried out for transitions with J < 15, K-, < 3, based on Watson’s reduced
quartic Hamiltonian 36 combined with Woods IAM calculation. The procedure
adopted in the centrifugal distortion treatment of CD3N0 was to first assume a set
of average rotational constants Ao, Bo and Co and fit the three independent variables
Ao, p = ](AaIa/IJ2 +(AbIa/Ib)213and p = arctan (&Ia/&fb) to selected A, E splittings
(as in table 19). An average transition frequency for the A and E components of a
doublet was then calculated from the quadrupole hypothetical centres of the
measured A-state lines. Rotational energies were generated by diagonalisation of
Watson’s reduced quartic Hamiltonian (12) in a I‘ symmetric top representation
H = AP,Z+BP~+CP~-A~P4-A~~P2P~-AKP~-26jP2(P~-P~)-
+
6#‘[Pz(P: -p,”) (P; - P;)P:]. (12)
The rotational and centrifugal distortion constants for CD3N0 were then obtained
by fitting the calculated centres of the A , E doublets. This whole process was then
recycled with improved Ao, Bo and Co constants, only one iteration being required.
The final fit to the A-state spectrum of CD3N0 is shown in table 21 and the derived
constants are given in table 22. High J and K-,, b-type transitions have been excluded
from the fit as indicated in table 21. As these transitions are potentially rich in
centrifugal distortion information, this exclusion limits the accuracy of the derived
constants. Therefore, accurate centrifugal distortion constants have been determined
from the spectra of sym-CH,DNO and sym-CHD,NO, analogous to our previous
treatment of aceta1dehyde.l For acetaldehyde, we showed that introduction of an
asymmetric CH2D or CHD, top causes localisation of the symmetric conformer.,
However, the spectra of the asymmetric species are still heavily perturbed due to
quantum mechanical tunnelling. The energy levels for sym-CH,DCHO and sym-
CHD,CHO, in the ground torsional state, could then be fitted using a rigid rotor
plus centrifugal distortion Hamiltonian. A few perturbations to the fit were observed
in sym-CH,DCHO arising through accidental degeneracies with levels of the
asymmetric species. In the present work, the quadrupole hypothetical centre
frequencies of sym-CH,DNO and sym-CHD,NO have been fitted to the eight
parameter Watson reduced quartic Hamiltonian (12), by diagonalisation of the energy
matrix in a I‘ symmetric top basis. Transitions perturbed by resonances with the
asymmetric forms have been excluded froin the fits as indicated in tables 23 and 24.
The quality of the fit over a wide range of J and K-, is excellent for both nitroso-
 View Article Online

552 MICROWAVE SPECTRUM OF NITROSOMETHANE

TABLE21.-HYPOTHETICAL
CENTRES AND CALCULATED FREQUENCIES (MHz) FOR A-STATE
TRANSITIONS OF CD3N0

C!h. vdbt Avobs-cslc

18 415.87 0.04 0.08

35 234.52 - 0.03 - 0.35
36 815.41 0.37 0.13
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35 967.30 1.70 0.45

37 692.91 0.13 0.19
36 112.19 -0.27 -0.14
21 659.29 -0.80 0.60
37 458.58 -0.63 0.19
35 092.94 - 1.65 -0.36
26 385.29 5.99 -0.21
8 627.40 - 7.34 -0.11
19 046.66 -3.26 0.12
12 937.14 - 10.41 -0.13
15 041.07 - 9.74 -0.45
18 102.52 - 13.53 -0.10
36 330.02 - 10.74 -0.56
24 116.66 - 16.38 0.00
25 013.68 14.85 -0.19
23 776.65 20.14 0.24
27 118.86 8.51 0.41
30 968.76 - 18.53 0.14
38 023.91 21.65 -0.65
16 247.63 - 28.38 - 0.43
8 494.78 - 2.54 -0.65
36 988.45 - 32.00 -0.18
25 927.71 3.94 -0.44
10 741.13 - 32.81 0.09
21 117.37 34.92 -4.90 C
20 182.26 44.00 - 5.40 C
14 689.58 -42.79 0.07
19 484.36 - 53.78 0.00
16 010.59 -29.61 6.02 C
18 301.90 - 51.37 6.94 c
25 165.52 - 65.34 -0.06
34 524.48 -22.65 6.97 C
37 937.26 - 54.64 8.17
34 621.51 82.22 - 11.78
34 760.03 79.27 -11.38
31 754.70 - 76.92 0.00
15 808.30 85.60 - 11.65
16 038.35 80.71 - 11.29 C
22 111.92 - 88.84 13.02
21 531.82 -76.67 12.13
30 021.30 147.97 - 11.72
29 989.19 149.24 - 11.99
21 121.70 - 161.51 3.82 C
26 781.10 - 196.36 4.61
Accurate to kO.05 MHz. Vdist = Vrigid-Ycalc using the constants of table 22. Transitions
not included in fit, see text.
 View Article Online

P . H . TURNER A N D A . P . COX 553

TABLE
22.-ROTATIONAL CONSTANTS (MHZ), CENTRIFUGAL DISTORTION CONSTANTS (kHz) AND
BARRIER PARAMETERS FOR THE TORSIONAL GROUND STATE OF CDiNO
A = 43 927.865k0.14
B = 9 638.078k0.04
C = 8 776.835k0.03

AJ = 9.7708 -t 0.8
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AJK= 150.4854-t 10.7

AK = 66.5474+ 15.2
dj= 0.9451& 0.03
6~ = -202.7162k3.1
p= 0.5152+0.005
/? = 0.1045+0.0003 rad
A0 = -240.763 k0.8 MHz
TABLE
23.-HYPOTHETICAL CENTRES AND CALCULATED TRANSITION FREQUENCIES ( M m ) OF
SYM-CH~DNO
Vh.0 a Vdist ’ -
AVobs calc

20 887.31 0.05 0.06

23 628.32 0.27 0.03
8 578.52 - 1.30 -0.05
32 370.86 4.95 0.18
14 293.66 - 1.58 -0.10
30 040.87 1.36 -0.06
21 428.82 - 1.25 -0.02
29 971.26 0.15 0.07
32 015.09 11.71 0.20
39 682.10 9.64 -0.04
23 716.29 10.28 0.06
19 999.49 2.25 -0.17
11 598.16 - 1.05 -0.10
32 794.89 12.01 0.04
16 931.61 1.24 -0.09
39 779.55 11.57 0.13
23 66Q.25 5.80 -0.01
34 678.52 15.45 0.19
31 676.51 17.21 0.05
35 404.69 30.83 -0.57
31 861.46 13.49 0.13
27 946.90 45.92 0.40
38 642.06 49.98 0.21
10 339.50 4.82 -0.29
30 064.19 18.51 31.73 C
31 032.66 17.29 - 24.90 C
14 689.25 12.04 -0.67 C
20 278.80 23.85 -2.36
14 690.82 48.37 0.10
12 133.27 48.61 -0.09
27 273.83 41.72 4.32 C
37 632.99 91.16 -0.17
33 758.06 89.29 -0.07
35 790.83 67.16 12.60
28 026.86 11.80 0.01
27 701.19 12.51 -0.03
4 Accurate to -t 0.05 MHz. l’&t = l’rigid-Vc,lc using the constants of table 25. C Transitions
perturbed (not included in fit) see text.
 View Article Online

554 MICROWAVE S P E C T R U M OF NITROSOMETHANE

methane species. Slightly more perturbations were observed in sym-CH,DNQ and

sym-CHD,NO compared with acetaldehyde l 1 and further study of these effects is
in progress. The rotational and centrifugal distortion constants for sym-CH,DNQ
and sym-CHD,NO are given in table 25.

TABLE
24. ?-HYPOTHETICAL CENTRES AND CALCULATED TRANSITION FREQUENCIES (MHZ) OF
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SYM-CHD2NO
vh.c a Vdist’ Avobs - CSIC

18 999.19 0.03 -0.05

37 990.91 0.32 -0.06
37 362.22 2.89 0.06
38 633.39 - 1.09 0.28
16 405.26 - 3.08 0.17
36 291.92 - 5.22 0.14
34 435.45 - 7.70 - 0.38
9 529.66 - 28.90 0.00
17 527.70 - 3 3.56 -0.38
13 338.44 - 39.68 0.02
17 225.25 - 36.54 0.46
17 778.38 -51.64 0.16
38 669.30 -43.95 - 0.86 C
22 844.82 - 64.44 - 1.00 c
30 329.15 45.08 0.06
34 669.55 57.62 0.07
37 085.69 27.81 0.09
25 536.44 - 77.68 -0.06
14 791.54 69.43 0.24
18 405.55 25.04 0.24
34 843.67 - 90.84 0.10
25 809.50 - 98.75 -0.60
18 573.09 - 10.82 -0.46
9 527.97 - 109.37 0.04
23 736.38 111.24 -0.37
23 072.78 133.53 -0.32
12 512.71 - 141.05 -0.02
16 074.69 - 177.63 0.04
20 250.00 -218.94 0.03
33 657.03 - 108.05 -2.56 C
35 719.91 - 176.76 - 3.06 C
25 066.40 -264.69 -0.03
30 053.39 258.02 0.17
30 159.53 250.41 0.30
30 542.13 -314.44 0.95 C
10 750.89 271.21 -0.01
10 913.25 259.58 -0.02
36 694.20 -367.58 3.51 C
8 604.69 -284.46 0.08
8 361.59 -267.07 0.16
28 021.78 -297.92 -0.14
27 665.07 -272.43 0.10
P See footnotes to table 23.
 View Article Online

P . H. TURNER A N D A . P . COX 555

TABLE
25.-ROTATIONAL CONSTANTS ( M H Z ) AND CENTRIFUGAL DISTORTION CONSTANTS (kHz)
FOR NITROSOMETHANE SPECIES
CD 3NO sym-CHDzNO sym-CH2DNO
U U U

A 43 927.865 k 0.14 51 006.404 2 0.14 51 434.673 k0.14

B 9 638.078 f 0.04 9 816.375 k 0.03 11 158.470 k0.03
C 8 776.835 & 0.03 9 182.894 k 0.03 9 728.824 f0.03
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AJ 9.7708k 0.8 7.0756k 0.8 11.1740k0.4

AJK 150.4854k 10.7 169.1122k 11.2 51.5194k5.8
AK 66.5474f 15.2 298.0859_+17.8 385.4784k 7.2
65 0.9451-L 0.03 0.6944+ 0.018 1.8317fi0.04
6~ -202.7162f 3.1 - 503.3225k 3.2 -76.4010+ 1.O
a From Woods-Watson treatment included for comparison.

HARMONIC FORCE FIELD

The centrifugal distortion constants for nitrosomethane species determined in the
present work and the recently reported vibrational fundamental assignment for
CH,NO in an argon matrix4 have been used together with the structural data to
determine a preliminary harmonic force field. Symmetry coordinates were used to
factorise the vibrational secular equation into one 8 x 8 A‘ block and one 4 x 4 A”
The available data enable only a minimal number of off-diagonal force
constants to be determined. The torsional mode, v12(A’’),was excluded from the
calculations. The procedure adopted therefore was to fit a valence force field to
the experimental values of AJ, ALKand aJ for CD,NO, sym-CH,DNO and sym-
CHD2N0 and the eight measured A’ vibrational fundamentals of CH3N0. Initially
a diagonal force field was assumed but a satisfactory fit was only obtained after the
introduction of the two off-diagonal force constants, f & ~ and ~ N O I L C N O The
.

TABLE
26.-vALENCE FORCE CONSTANTS a FOR CH,NO
diagonal constant interaction constant
value description value description

4.804 C-H str. 1.51f0.3 C-N/N=O

0.501 HCH bend -0.31 k0.05 N=O/CNO
0.527 HCN bend
3.51 k0.07 C-N str.
9.87f0.4 N-0 str.
2.04k0.09 CNO bend
a Force constants in units of mdyn A-l, mdyn A rad-2 and mdyn rad-’ as appropriate.

TABLE
27.-oBSERVED AND CALCULATED a DISTORTION CONSTANTS (kHz) FOR NITROSOMETHANE
SPECIES
CH3NO sym-CH2DN0 sym-CHDzNO CD 3N0
obs. calc. obs. calc. obs. calc. obs. calc.

AJ 12.346 11.1740 12.314 7.0756 8.878 9.7708 8.754

AK 645.814 385.4784 363.373 298.0859 373.849 66.5474 222.210
SJ 1.571 1.726 1.8317 1.980 0.6944 0.791 0.9451 0.974
a From force field determined in present work. b Observed SJ from A , E centre frequencies of
Q-branch, El = 1 lines fitted with Kivelson-Wilson distortion term ~ ~ J J ~1)”.
( J +
 View Article Online

556 MICROWAVE SPECTRUM OF NITROSOMETHANE

interaction constantf&,LcNo was found to be very small. The set of force constants
finally chosen is given in table 26 and the calculated centrifugal distortion constants
are compared with the observed values in table 27. The observed A,, AK and aJ
distortion constants for sym-CH,DNO and sym-CHD,NO and AJ and 6, for CD3N0
agree well with the calculated values from the force field. The small discrepancies
between the observed and calculated distortion constants point to deficiences in the
determined force field ; better agreement between observed and calculated distortion
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constants was obtained for acetaldehyde,l where a much more complete force field
is a~ailable.~' The poor fit for AK in CD3N0 (see table 27) is indicative of the
difficulties of carrying out a centrifugal distortion treatment in the presence of internal
rotation rather than any serious errors in the force field. Transitions sensitive to the
value of this constant in CD3N0 involve high K - l , b-type lines for which it is difficult
to obtain accurate centres of the A , E doublets.

DISCUSSION
The NO bond length of 1.211 A in nitrosomethane is close to the value of 1.20 A
expected for a NO double bond 41 and is virtually identical to the NO bond length
of 1.212A found in HN0.42*43 In contrast, the NO bond lengths in the nitrosyl
halides are all abnormally short, the values being, 1.136, 1.139 and 1.146 A along the
series fluoride,44 chloride 45 and respectively. (cf. 1.151 A in NO).47
These variations in NO bond length are also substantiated by vibrational data;
1.250 t.

z
TT
1.150 - BrNO xN0
~\NO,NO
I- 'INo FNO

1.100 I I 1 I I I 1 I
1500 1600 1700 1800 1900
v(N=O)/cm-'
FIG. 4.-Bond length-stretching frequency correlation for N=O bonds. (CH&NNO : A.
Guarnieri, F. Rohwer and F. Scappini, 2. Naturforsch., 1975, 30a, 904 ; I. W. Levin, G. W. A.
Milne and T. Axenrod, J. Chem. Phys., 1970,53,2505. CH3N0: Present work ; A. J. Barnes,
H. E. Hallam, S. Waring and J. R. Amstrong, J.C.S. Faruday 11, 1976, 72, 1. HNO: S. Saito
and K. Takagi, J. Mol. Spectr., 1973,47,99 ; F. W. Dalby, Canad. J. Phys., 1958,36,1336 ; M. E.
'
Jacox and D. E. Milligan, J. Mol. Spectr., 1973, 48, 536. CF3N0: P. H. Turner and A. P. Cox,
Chem. Phys. Letters, 1976,39,585 ; H. F. Shurvell, S. C. Dass and R. D. Gordon, Canad. J. Chem.,
1974, 52, 3149. cis-HNOz : A. P. Cox, A. H. Brittain and D. J. Finnigan, Trans, Furaday Soc.,
1971,67,2179 ; lo G. E. McGraw, D. L. Bernitt and I. C. Hisatsune,J. Chem. Phys., 1966,45,1392.
trans-HN02 : ref. (9) ; ref. (10). BrNO : l 1 D. J. Millen and D. Mitra, Trans. Faraday SOC., 1970,
66, 2414; l2 W. G. Bums and H. J. Bernstein, J. Chem. Phys., 1950, 18, 1669. ClNO: l 3 D. J.
Millen and J. Pannell, J. Chem. SOC.,1961, 1322 ; ref. (12). FNO : l4 K.S. Buckton, A. C. Legon
and D. J. Millen, Trans. Faraday SOC.,1969,65,1975 ; l5 R. L. Cook, J. Chem. Phys., 1965,42,2927.
Nz03: l6 A. H. Brittain, A. P. Cox and R. L. Kuzckowski, Trans. Faruday Soc., 1969, 65, 1963 ;
l 7 J. P. Devlin and I. C. Hisatsune, Spectrochim. Acta, 1961, 17, 218. NO : l8 J. J. Gallagher and
C. M. Johnson, Phys. Rev., 1956, 103, 1727 ; l9 H. H, Nielsen and W. Gordy, Phys. Rev., 1939,
56, 781.
 View Article Online

P . H . T U R N E R AND A . P . COX 557

fig. 4 shows the correlation between NO bond length and the frequency of the NO
stretching vibration. Further support for a normal structure for CH3N0 comes
from the C-N bond length of 1.480 A which is similar to 1.471 A in CH3NH24 8
and 1.489A in CH3N024 9 (cf. 1.51 A in CF,NO).* The CNO angle of 113.2' in
CH3N0 is typical for XNO molecules [see table 10 of ref. (6)]. Two notable excep-
tions however are HNO (108.6' in the ground electronic state)42*43 and N203(105.1')7
and 1.489A in CH3N0249(cf. 1.51A in CF,NO).* The CNO angle of 113.2'
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in CH,NO is typical for XNO molecules [see table 10 of ref. (6)]. Two notable
exceptions however are HNO (108.4" in the ground electronic state)42*43 and
N203(105.1'),' which has a very weak central N-N bond.

TABLE
28.-cHANGES OF DIPOLE MOMENT (D) ON METHYLATION
molecule Pobs ref. molecule Pobs ref.

HNO 1.67 1 HC=CH 0

CH3NQ 2.320 2 CH3CrCH 0.75 6
HZCO 2.339 3 HNFz 1.93 7
CH3CHO 2.750 2 CH3NF2 2.57 8
(CH3)ZCO 2.90 4
cisHONO 1.423 9
HCN 2.986 5 cisCH30NO 2.05 10
CH3CN 3.94 6
S. Saito and K. Takagi, J. Mul. Spectr., 1973, 47, 99. Present work. J. N. Shoolery and
A. H. Sharbaugh, Phys. Rev., 1951, 82, 95. J. D. Swalen and C. C. Costain, J. Chem. Phys.,
1959, 31, 1562. B. D. Bhattacharya and W. Gordy, Phys. Rev., 1960, 119, 144. S . N. Ghosh,
R. Trambarulo and W. Gordy, J. Chem. Phys., 1953, 21, 308. ' D. R. Lide, Jr., J. Chem. Plzys.,
1963,38,456. L. Pierce, R. G. Hayes and J. F. Beecher, J . Chem. Phys., 1967,46,4352. A. P.
Cox, A. H. Brittain and D. J. Finnigan, Trans. Furaday Suc., 1971, 67, 2179. l o D. Stelman, Diss.
A h . , 1965, 25, no. 64-9094.

The increase of dipole moment on methylation of HNO is similar to the observed

increase of dipole moment on methylation of several other molecules (see table 28).
CND0/2 calculations on formaldehyde, hydrogen cyanide and acetylene O have
shown that this effect is associated with charge alternation. Most of the rearrange-
ment of charge on methyl substitution occurs in the n-system according to this theory.
The orientation of the dipole moment in acetaldehyde, determined in the present

H hj

FIG.5.-Orientation of the dipole moment in acetaldehyde.

 View Article Online

558 M I C R O W A V E SPECTRUM O F N I T R O S O M E T H A N E

work to lie exterior to the CCO angle by 10.1" (see fig. 5), is consistent with this
charge alternation. A similar redistribution of charge within the n-system of the
NO group of CH3N0 would also explain the increase in dipole moment over HNO.
The direction of the dipole moment in CH3N0 again lies exterior to the CNO angle,
but in this case the orientation is modified appreciably by the highly directional lone
pair on nitrogen.
The large positive xcc values of 5.52 MHz for nitrosomethane,l 3.78 and 3.55 MHz
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in cis and trans nitrous acids respectively and 5.10 MHz in HNO 4 2 (the only
principal axis components of the quadrupole coupling tensor determined for these
molecules) are difficult to reproduce using simple valence bond structures. However,
good fits result if the a-bond i o n i c i t i e ~ ,i,~ ~for X-N and N-0 and the ionic
character in the N-0 n-bond, in, are introduced into the usual Townes-Dailey
quadrupole coupling formalism.52
For CH,NO, an in value of 0.23, which implies an effective out-of-plane p-orbital
population at nitrogen of 0.77 electrons, is sufficient to give the experimental xcc.
The decreased values of xcc for the nitrous acids are then mainly due to the ionic
characters, in, in the Q-N and N=O bonds operating in different directions compared
with the C-N and N-0 bonds in CH3N0. The smaller value of xcc for HNO
compared with CH3N0 is accounted for, in terms of this model, by a slightly reduced
in value of 0.19. Differences in (r bond orbital hybridisation at nitrogen between
CH3N0 and HNO and the i, values for C-N and H-N alone do not account for
the difference in xcc values for the two molecules. A smaller out-of-plane p-orbital
population at nitrogen in CH3N0 compared with HNO, as suggested by the quad-
rupole coupling data, would also be consistent with a n-polarisation occurring in the
N=O group of CH3N0 and the larger dipole moment for this molecule.

We thank the S.R.C. for a Research Studentship for one of us (P. H. T.).
We also thank Mrs. Ch. Dyllick-Brenzinger and M. P. Landy for their assistance.
Helpful discussions with Prof. J. E. Boggs and D. Coffey, Jr., are also much
appreciated.

D. Coffey, Jr., C. 0. Britt and J. E. Boggs, J. Chem. Phys., 1968, 49, 591.
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l7 H. H. Nielsen, Phys. Rev., 1932, 40,445.
l8 D. G. Burkhard and D. M. Dennison, Phys. Rev., 1951, 84,408.
l9 J. K. Bragg and S. Golden, Phys. Rev., 1949, 75, 735.
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21 F. J. Wodarczyk and E. B. Wilson, Jr., J. Mol. Spectr., 1971, 37, 445.
22 Symposium on Molecular Spectroscopy, Columbus, Ohio, 1969, paper R6.
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 View Article Online

P . H . T U R N E R A N D A . P. C O X 559
25 P. H. Turner, Ph. D. Thesis (Bristol, 1976).
26 W. H. Kirchhoff, J . Amer. Chem. Sac., 1967, 89, 1312.
27 D. R. Lide, Jr., J. Chem. Phys., 1952, 20, 1761.
2 8 J. Kraitchman, Amer. J. Phys., 1953, 21, 17.
2 9 A. Chutjian, J. Mol. Spectr., 1964, 14, 361.
30 L. Nygaard, J. Mol. Spectr., 1976, 62,292.
31 V. W. Laurie and D. R. Herschbach, J. Chem. Phys., 1964, 40, 3142.
32 R. H. Schwendeman and J. D. Kelly, J. Chenz. Phys., 1965, 42, 1132.
Published on 01 January 1978. Downloaded by Brown University on 30/10/2014 14:22:15.

3 3 E. Hirota, J. Chem. Phys., 1966, 45, 1984.

34 J. E. Wollrab, Rotational Spectra and Molecular Structure (Academic Press, N.Y., 1967).
35 R. C. Woods, J. Mol. Spectr., 1966, 21, 4.
36 J. K. G. Watson, J. Chem. Phys., 1967, 46, 1935.
37 H. W. Kroto and B. M. Landsberg, J. Mol. Spectr., 1976, 62, 346.
38 E. A. Valenzuela and R. C . Woods, J. Chem. Phys., 1974,61,4119.
39 see H. F. Shurvell, S. C. Dass and R. D. Gordon, Canad. J. Chem., 1974, 52, 3149.
40 H. Hollenstein and Hs. H. Giinthard, Spectrochim. Acta, 1971, 27A, 2027.
41 L. Pauling, The Nature of the Chemical Bond (Cornell University Press, Ithaca, 1960).
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43 F. W. Dalby, Canad. J. Phys., 1958, 36, 1336.
4 4 K. S. Buckton, A. C. Legon and D. J. Millen, Trans. Faraday SOC.,1969, 65,1975.

45 D. J. Millen and J. Pannell, J. Chem. SOC.,1961, 1322.

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