JOURNAL OF MOLECULAR SPECTROSCOPY 97, 154- 164 ( 1983)

The Pure Rotational Spectrum of Diazomethane, H&NN,

in the Millimeter Wave Region

ECKHARD SCHAFER’AND MANFRED WINNEWISSER

Physikalisch-ChemischesInstitut,JustwLiebig-Universitdt Giessen, Heinrich-Bu$-Ring 58,
D-6300 Giessen, West Germany

The rotationalspectrumof diazomethane,H2CNN,wasinvestigatedin the frequencyrange

100to 400GHz. Due to the C,. symmetryof the molecule,whichis planar,only a-type dipole
transitions were observed. The measurements were analyzed using Watson’s S-reduced Ham-
iltonian. A detailed centrifugal distortion analysis yielded the following rotational and quartic
centrifugal distortion constants: A = 272 979.1(8. I) MHz, B = 11 305.42697(45) MHz,
C = 10 845.22028(47) MHz, D, = 4.14620(74) kHz, D,K = 396.817(92) kHz, DK = 22.0 MHz
(fixed), C = -192.55(42) kHz, dz = -57.27(39) Hz. Some sextic and higher-orderdistortion
constantsweredeterminedand are discussed.

I. INTRODUCTION

Diazomethane, H$NN, belongs to a group of isomers, the structures of which are

given in Fig. 1, and for which only limited gas-phase spectroscopic information is
available. In some recent work we reported precision spectroscopic data in the mil-
limeter wave region on isocyanamide, H2N-NC (I, 2) one of the isomers of diazo-
methane. In order to recognize and assign the spectrum of isocyanamide we wanted
to know the pure rotational spectrum of H&NN in the millimeter wave region from
100 to 400 GHz. However, microwave information available on H$NN prior to
our investigation was very limited. Cox et al. (3) in 1958 reported the values for
(B,, + Co) and (& - Co) for three isotopic species of diazomethane, namely, H&NN,
HDCNN, and D$YNN, which were obtained from measurements in the frequency
range 19 000 to 90 000 MHz. No absorption frequencies were reported. In 1962
Sheridan (4) reported the extension of this earlier work to further isotopic species of
diazomethane containing the isotopes 13C, “N, and D. The molecular structure pa-
rameters were also discussed together with nuclear quadrupole splitting due to the
two nitrogen nuclei. Again, no absorption frequencies were reported.
These early microwave measurements were in agreement with a planar molecular
structure of diazomethane as were numerous infrared investigations (5-10). Moore
(9) determined the A rotational constant from medium-resolution infrared data. This
information together with the early microwave B. and Co values (3, 4) led to a
reasonable prediction of the millimeter wave spectrum of H&NN. In this paper we
report the detection of the a-type rotational spectrum of the main isotopic species
of HzCNN in the frequency range 100 to 400 GHz, thus providing the precision data

’ Part of the author’s Dissertation, Justus-Liebig-Universitit Giessen (D26).

0022-2852/83/010154-l 1$03.00/O 154

Copyright8 1983 by Academic Press, Inc.
All rights of reproduclion in any form reserved.
 ROTATIONAL SPECI-RUM OF DIAZOMETHANE 155

HCN=C=N
/" +!
H( 'N

needed for a radioastronomical search, These data have already proved very useful
in assigning the resolved rotational structure of the infrared spectrum of H&XN,
which has been recently measured in our laboratory (II).

II. EXPERIMENTAL PROCEDURES

(1) chemical Pre~ffr~tion of ~~~~~

The chemical synthesis followed the method of Pechmann (12):

N--CH,
O=C= + KOH - H$XN -t Hz0 + KNCO.

Ten grams of a 50 to 60% aqueous solution of potassium hydroxide is chilled and

solidified at -50°C in a lOO-ml two-necked flask. Two grams of ni~~rne~yl urea
is deposited on top of the KOH-ice mixture. While the flask is evacuated and flushed
with nitrogen at 300 Pa, the mixture is allowed to warm up and is stirred as soon as
it becomes liquid. The reaction indicated above begins at a temperature of - 15°C
and is finished after approximately two hours . The volatile reaction products contain
mainly H#XN and Hz0 which are trapped separately. The explosive diazomethane
is carefully distilled into sample tubes and stored at liquid nitrogen temperature.

(2) The ~~m~l~irneter Wave ~~~trometer

The observation of the rotational spectrum of HZCNN was carried out witb a newly
built submillimeter wave spectrometer designed for the detection of unstable species
(2, 13). The absorption cell is a free space cell 1.5 m in length and with 10 cm inner
diameter. The submillimeter wave radiation in the frequency range 100-800 GHz is
produced by frequency multipli~tion of the 50- to 85-GHz fun~en~ frequency
of one of the millimeter wave klystrons employed. Details of the spectrometer system
will be described elsewhere (13). However, it should be mentioned that our spec-
trometer has two modes of operation. The first mode of operation is fast sweeping
of the microwave source with video display, signal averaging, and computer data-
156 SCHAFER AND WINNFWISSER

processing, employing a frequency drift stabilization of the free-running klystron (13,

14). The second mode of operation employs source modulation and phase-sensitive
detection. In this mode the klystron frequency is phase-locked and frequency mod-
ulated with 3.2 kHz. The output signal of the lock-in amplifier can either be recorded
or averaged in the same signal averager. Employing the system in the latter mode
with second-derivative recording, a survey scan of diazomethane for the J = 11 -
10 transition at 243 100 MHz is shown in Fig. 2. This spectrum shows an excellent
signal-to-noise ratio, so that many lines arising from excited vibrational states can
be observed. The absolute frequency accuracy of unblended lines is estimated to be
better than +30 kHz in the entire millimeter and subm~meter range. All measure-
ments were carried out at room temperature with total pressures in the absorption
cell of about 1 to 2 Pa. The decomposition was at first fast, with a half-life of about
5 min. But after the Pyrex-absorption cell was coated with a polyethylene layer due
to the polymerization of the CH2 radicals the observed half-life increased to more
than 20 min. Experiments with a metal cell revealed a half-life of about 10 seconds.

III. MEASURED ROTATIONAL TRANSITIONS AND

CENTRIFUGAL DISTORTION ANALYSIS

The observed spectrum showed the characteristic pattern of u-type W-branch ro-
tational transitions as shown in Fig. 2. Of course, the asymmetry splitting of the
KG= 1 lines is considerably larger than the frequency range covered in Fig. 2
and therefore these lines are not shown. The intensities of the rotational transitions

“011-‘0010 , $3.9 “3.8

3.8 y3.7
115-x)5

114-104
/ ?d02,8
116-106
/

r
I I r I

243300 243400 243500 243600 24,kOO MHz

ll+-107

llg-10g 118108

I1 I I I. ., L 1
1 1 .

, I 1 I 1
242800 242900 243000 243100 243200 MHZ

FIG. 2. Survey scan of part of the observed millimeter wave spectrum of diazomethane at 243.6 GHz
with the typical K, pattern of a slightly asymmetric rotor. The recording was obtained using source mod-
ulation of the klystron frequency and second-harmonic phasssensitive detection.
 ROTATIONAL SPECTRUM OF DIAZOMETHANE 157

1.90

160

140

I20

100

80

60

40
-100
20

0
-1 0 I

FIG.3. Simulated absor@ionprofile of the nuclear quadrupolebyperfmepattern of the 1093+- 99,,

transitionat 220 751.855 MHz. The assumed line width is 0.35 MHz. The nuclear quadrnpolecoupling
constantswen made available to us through the courtesy of Dr. Cox (15). They are xJN( I)] = -1.19
MHZ;dN(l)] = -1.04 MHz, h[N(Z)] = -1.73 MHZ;&N(2)] = 5.15 MHz. The quadrupolarsbiA
is expressedin MHz.

follow a slightly prolate asymmetric rotor distribution modulated by spin statistics

due to the two identical hydrogen nuclei. The molecular symmetry group is Cz,,
so that transitions in the ground state arising from odd Kn levels have three times
the statistical weight of those arising from even K, levels. For transitions with
-K, = J or J - 1 broadening of the spectral lines due to nuclear quadrupole splitting
due to the two nitrogen nuclei was noticeable. However, the multiplet structure could
not be resolved. Cox in 198 1 (15) has communicated to us the results of his quad-
rupole analysis using low Jtransitions. For the central nitrogen in H&BIN he obtained
the values h = - 1.19 MHz and x~ = - 1.04 MHz and for the end nitrogen the
values xaa = - 1.73 MHZ and xbb = 5.15 MHZ. Using these nuclear quadrupole
coupling constants we simulated the hyperhne pattern of the 109,z- 99,1 rotational
transition at 220 75 1.855 MHz, for which the splitting may be expected to be a
maximum among all the lines measured. The absorption profile consists of a super-
position of nine individual hyperhne components having more than 1% intensity
(hF; AF’ = + 1 transitions). in Fii. 3 this simulated line profile is shown. From Fig.
3 we can conclude that the displacement of the unperturbed line from the center of
the simulated line profile is of the order of 50 kHz. Since our measuring accuracy is
about +30 kHz, we have not made any corrections to our measured line positions.
Table I gives the measured and calculated line positions of all of the observed
rotational transitions. It was not possible to resolve the & = 3 asymmetry doublet
splittings for J < 11. The asymmetry doublets of all higher Kg components could
not be resolved at all and most of these line frequencies were assigned and fitted to
just one of the doublet transitions. Table I also contains the line frequencies com-
municated to us by Cox (15) with the weighting factors used in the present fit. All
together 142 individual line frequencies have been analyzed using Watson’s S-reduced
H~to~an in the f’ axis representation (16) with a standard deviation of 22.4 kHz,
which corresponds to the assumed accuracy of the frequency measurements.
 TABLE I

Observedand Calculated Frequencies of Diazomethane

Transitions Frequencies / MHz ohs.-cal. Weights

J(K,,KcI- JfK,,KcI observed calculated(Std.7Jev.t /kHr Ref.

11 0, l)- O( 0” 0) 22150.68 22150.6307(071 49.3 a (15)

2f a, 2t- I( a, If 44300.5% 44300.556iff31 24.9 a fl5)

21 1, 2)- l( 1, 1) 431139.47 43%39.3?21(143 97.9 0 (151
2t 1, II- 1( 1, 0) 44769.7?32(13)

3f 0, 3)- 2( 0, 2) 66448.92 66449.0672120f -147.2 0 (15)

3f 1, 3!- 2( 1, 2) 65758.4419(20)
3( 1, 2!- 2( 1, 1) 6713 8.68 67139,0199120) -339.9 0 (161
3( 2, 2)- 2( 2” 1) 66441.92%9(17)
3( 2, l)- 2( 2, 0) 66444.344?(17)

4( 0, 4)- 3( a. 31 88595.20 88595.4609(26) -260.9 0 (151

4( 1. 4)- 3( 1, 31 %7676,?730(26!
4( 1, 3f- 3f 1, 2) 89517.56 %9517*49%3(25) 61.7 a (15)
PI 2, 3)- 3( 2, 2) 88583.24 %%588.30911213 -69.1 a (15)
4( 2. 2)- 3( 2, 11 88594.37 88594.3482(211 21.8 0 (15)
4( 3, 2)- 3( 3, 11 88574.34 8%573.8460(23) 494.0 a (15)
4f 3. It- 3f 3, 01 88574.34 %~673.%489~23~ 491.f a (151

5I 0, 5)- 4f 0, 41 110739.a4a lio73Q.o3o4~311 9.6 I

5f I, s)- 4( 1, 41 109594.070 109594.1203 (31) -50.3 1
5( 1, 4)- 4( 1, 3) 111894.946 111%Q4.9509(31) -4.9 1
5( 2, 4)- 4( 2, 3) 110733.934 110733.8925(26) 41.5 I
5( 2. 3)- 4f 2, 21 110745.992 110745.9703(26) 21.7 1
5( 3, 3f- 4f 3, 2) 110717.159 1107~7.1290(2%~ 30.0 a.5
5( 3, 2)- 4( 3, 11 110717.159 110717.1394(28~ 19.6 0.5
5( 4. l)- 4( 4, 0) 110687.7074(27)

61 0. 61- 5l a, 5) 132879.0700(35)
6f I, 6t- 51 f, 51 131510.2397(363
61 1. 5t- 6f 1, 41 1342fl.il96135)
6( 2. 51- 51 2, 41 13287%.4801(29~
6f 2, 4)- 6f 2, 3) 132899.6160(29)
6( 3, 4)- 5f 3, 3) 132860.2905(33)
6f 3, 3)- 61 3, 2) 132%60.3180(333
6f 4, 2)- 5f 4, 1) 132824.60691311
6( 5. l)- St 5, 01 132778.76061361

7( 0, 7)- 6( a, 61 155014.%752(3%1
7( 1, 7)- 6( 1, 6) 153424.%884(39)
7t 1, 6f- 6( 1, 51 156645.7460(39)
71 2, 6t- 6( 2, Si 155021.8727132~
71 2, 5)- 6f 2, 4) 155055.6857 (32)
If 3, 5t- 6( 3, 4) 155003.3031(36)
7( 3, 4)- 6( 3, 31 155oa3*365a~36~
7f 4, 4t- 6f 4, 31 154961.1562~35)
 ROTATIONAL SPECTRUM OF DIAZOMETHA~ 159

TABLE I-Continued

Transitions Frequencies / MHz ohs.-cal. Weights

J(K,,K,)- J(K,.K,) observed calculatedfStd.Dev.) /kHz Ref.

7( 5, 3)- 6( 5, 2) 154907.4466(40)
7( 6, 2)- 6( 6, 1) 154840.2771(47)

8( 0, al- 7( 0, 7) 177145.695 177145.7418(41) -46.8 1

8( 1, a)- 71 1, 7) 175337.827 175337.8252(42) 1.8 1
81 1, 7)- 7( 1, 6) 179018.577 179018.5663(41) 10.7 1
8( 2, 71- 7( 2, 6) 177163.865 177163.8714(341 -6.4 1
8( 2, 6)- 7( 2, 5) 177214.580 177214.5851(341 -5.1 1
8( 3, 6)- 71 3, 51 177146.189 177146.1385f391 50.5 0
8( 3, 5)- 7( 3, 4) 177146.189 177146.2623(39) -73.3 0
8( 4, 5)- 71 4, 41 177097.300 177097.2968(38) 3.2 1
a( 5, 4)- ff 5. 3) 177035.607 177035.6214f44) -14.4 1
8( 6, 3)- 7f 6, 21 176958.740 176958,71X6(50) 28.4 I
8( 7, 2)- 7( 7. 1) 176864.131 176864.1082155) 22.8 1
9( 0. 9)- 81 0, 8) 199270.971 199270.9677(43) 3.3 1
9( 1, 9)- 8( 1, 8) 197248.812 197248. 8106(44) 1.4 1
9( 1, a)- a( 1, 7) 201389.310 201389.3209(43 I -10.9 1
9( 2, a)- a( 2, 7) 199304.2771(35)
9( 2, 7)- 8( 2, 6) 199376.718 199376.7141(35) 3.9 1
9( 3, 7)- 8( 3, 6) 199288.881 199288.7662(41) 114.8 0
91 3, 6)- 8( 3, 5) 199288.881 199288.9931(41) -112.1 0
9I 4, 61- 8( 4, 5) 199232.974 199232.9704(40) 3.6 1
9( 5, 51- 8( 5, 4) 199163.213 199163.2120(46) 1 1
91 6, 4)- 8( 6, 31 199076.496 199076.5039151) -7.9 1
9( 7, 3)- 81 7, 2) 198969,995 198969.9811(571 13.9 1

lO( O,lOf- 9( 0, 9) 221389.857 221389.8525(441 4.5 1

101 I.lO)- 9[ 1, 9) 219157.650 219157.6070(451 43.0 t
lO( 1, 9)- 9( 1, 8) 223757.725 223757.7445(441 -19.5 1
IO{ 2, 91- 9( 2. 8) 221442.895 221442.8907(35) 4.3 1
lO( 2, a)- 9( 2, 7) 221542.470 221542.4718(35) -1.8 1
10( 3, 8)- 9( 3, 7) 221431.348 221431.1540(431 194.0 0
lO( 3, 7)- 9( 3, 6) 221431.348 221431.5430(43) -,195.o 0
lO( 4. 7)- 9( 4. 6) 221368.109 221368.1185(42) -9.5 1
1Di 5, 6i- 9i 5; 5j 221290.156 221290.1453(47) 10.7 1
lO( 6, 5)- 9( 6, 4) 221193.586 221193.5739(52) 12.1 1
lO( 7, 4)- 9( 7, 3) 221075.098 221075.0984~57) 4 1
lO( 8, 3)- 9( 8, 2) 220930.233 220930.2443(61) -1;:3 1
lO( 9, 2)- 9( 9, 1) 220751.855 220751.8397(82) 15.3 1

lit O,lll-lD( 0,101 243501,707 243501.6989(45) 8.1 1

1lC l,lll-101 1,lO) 241063.971 241063.9792(45~ -8.2 1
111 l,lO)-1Ol I, 9) 246123.569 246123.5705~45~ -1.5 I
11( 2,10f-IO{ 2, 9) 243579.528 243579.5136(35) 14.4 I
11( 2, 9)-IOf 2. 8) 243712.256 243712.2541(35) 1.9 1
Ilf 3. 91-IOf 3, 8) 243573.237 243573.2675(44) -30.5 1

where p, px,, F,,, and p, are the operators for the total angular momentum and its
components, respectively. The ladder operators are given by F* = iX + ijy. The
constants A, B, and C are Watson’s reduced rotational constants in the I’ axis rep-
resentation. In order to fit the rotational lines arising from high Z&-rotational levels,
it was found necessary to introduce higher-order centrifugal distortion terms. The
reduced spectroscopic constants in the I’ axis representation are given in Table II.
It should be pointed out that the value for & was obtained from the infrared work
of Moore (9) and was held tixed in the fit.
160 SCHiiFER AND WINNEWISSER

TABLE I-Continued

Transitions Frequencies I ?4Hz ohs.-Cal. Weights

J(K,,Kcf- JIK,,Kc) observed calcu1atedCStd.Dev.l /&Hz Ref.

111 3. 8)-lO( 3. 71 243573.926 243573.8996f44) 26.4 1

ll( 4; 8)-lO( 4; 7j 243502.705 243502.6825(43 1 22.5 1
ll( 5, 7)-lO( 5, 61 243416.350 243416.3483(48) 1.7 1
ll( 6. 6)-lO( 6, 5) 243309.829 243309.8412(51) -12.2 1
llf 7. 51-101 7. 41 243179.392 243179.37611571 15.9 1
Iii 8; 4j-1Oi 8; 3j 243019.996 243019.9775~60~ 18.5 1
flf 9, 3)-lO( 9, 21 242823.725 242823.7383(80) -13.3 1
ll(10, 2f-lO(10, 1) 242576.495 242576.4897(1391 5.3 1

12( 0,12)-ll( 0,111 265605.828 265605.8135(47) 14.5 1

12( 1,12)-ll( 1,ll) 262967.700 262967.6944(46) 5.6 1
12( 1,11)-ll( 1,101 268486.529 268486.5298(46) 8 1
12( 2.111-llf 2.10) 265713.944 265713.9467(351 -;:7 1
12i P;lOj-lli 2; 9j 265886.459 265886.4533(361 5.7 1
12( 3.101-111 3, 91 265715.067 265715.0697(44) -2.7 1
121 3. 9)-ll[ 3. 81 265716.071 265716.05281441 18.2 1
12i 4; 9)-lli 4; Si 265636.616 265636.6039(433 12.1 1
12( 5. 8)-ll( 5, 7) 265541.737 265541.7477(49) -10.7 1
12( 6, 7)-ll( 6, 6) 265425.183 265425.2254150) -42.4 1
12( 7, 6)-ll( 7, 5) 265282.719 265282.7303(56) -11.3 1
12( 8. 5)-ll( 8, 4) 265108.772 265108.7703(59) 1.7 1
12( 9. 4)-11( 9, 3) 264894.688 264894.6981(?7) -10.1 1
12(10. 3)-ll(10, 21 264625.0569(~23)
12(11. 2)-ll(11, 1) 264269.3154(184)

13( 0,13)-12( 0,12) 287701.514 287701.5080(52) 6.0 1

13( 1,13)-12( 1,121 284868.515 284868.5226(47) -7.6 1
13( 1,12)-12( 1,ll) 290846.347 290846.3508(48) -3.8 1
13( 2,12)-12( 2,111 287846.008 287845.9914(37) 16.6 1
13f 2,11)-12( 2.10) 288065.443 288065.4565(38) -13.5 I
13( 3,ltl-121 3,lO) 287856.512 287856.5209(44) -8.9 I
13( 3,101-12( 3, 91 287857.957 287857.9954(44) -38.4 1
13( 4,10)-12{ 4, 9f 287769.839 287769.8241(44) 14.9 0.5
13( 4, 91-121 4, 8) 287769.839 287769.8278(44) 11.2 0.5
13( 5, 9)-12( 5, 8) 287666.244 287666.2706149) -26.6 1
13( 6. 8)-12( 6, 7) 287539.627 287539.6463(50) -19.3 1
13( 7. 7)-12( 7, 6) 2 873 85.045 287385.0770(56) -32.0 1
13( 8. 6)-12( 8, 5) 287196.508 287196.5372(60) -29.2 1
131 9. 51-121 9. 41 286964.637 286964.6338(76) 3.2 1
13(10; Ot-X(10; 3j 286672.657 286672.6220(10~) 35.0 1
13C11, 31-12111, 21 286287.391 286287.443211543 -52.2 1

14( 0,14)-13( 0,13) 309788.085 309788.1005t59) -15.5 1

14( 1,14)-13( 1,131 306766.235 306766.2366(51) -1.6 1
14( 1.13)-13( 1,12) 313202.756 313202.7590(52) -3.0 1
14( 2.13)-13( 2,121 309975.451 309975.4490(42) 2.0 1
14( 2,121-13( 2.11) 310249.631 310249.6442(42) -13.2 1

IV. DISCUSSION

The pure a-type rotational spectra of nearly symmetric prolate rotors contain in-
formation only about the difference (A - 2&). Since we held DK fixed at its infrared
value in the least-squares analysis, the uncertainty of +5 MHz in & would lead to
an error of +13 MHz for A, somewhat larger than that calculated from the least-
squares analysis and given in Table II. However, the A constant is considerably more
reliably determined than from the existing ir data alone. The higher-order centrifugal
 ROTATIONAL SPE~R~M OF DIAZOM~THANE 161

TABLE I-Continued

Transitions Frequencies / MHz obs .-Cal* Weights

J(Ka,K,J- J(Ka,K,f observed calculatedfStd.Dev.) /kHz Ref.

14 ( 3,12)-13( 3,ll) 309997.565 309997.5786(44) -13.6 1

14 ( 3,11)-13( 3,lO) 309999.706 309999*7231(453 -17.1 1
14 ( 4,11)-13( 4,101 309902.280 309902.2844(45) -4.4 0.5
14( 4,10)-13( 4. 9) 309902.280 309902.2908(45) -10.8 0.5
14f 5,10)-13( 5, 91 309789.846 309789.8438(51) 2.2 1
141 6, 9)-13f 6, 8) 309653.013 309653.02361521 -10.6 1
14( 7. 8)-13f 7, 7) 309486.332 309486.33211601 1 1
14f 8, 7)-13( 8, 61 309283.215 309283.1925(641 2;:5 1
14f 9, 61-13( 9, 5) 309033.476 30~033.4599~80~ 16.1 I
14110, 5f-13(10, 41 308719.128 308719.1015(97~ 26.5 I
14(11, 4)-13(11, 31 30#04.583 30~~4.5352(163) 47.8 1

15[ 0,15)-141 0,141 331864.923 331964.9175f7lf 5.5 1

15( 1,15)-141 1.141 328660.644 328660.6127(583 31.3 1
151 1,14)-14( 1.131 335555.470 336555~4767(60~ -6.7 1
15f 2,14)-14( 2.13) 332102.130 332102.1211(50) 8.9 1
15( 2,13)-14( 2,121 332439.387 332439.3888(51! -1.8 1
15( 3,13)-14( 3,121 332138.205 332138.1972(46) 1
15( 3,12)-14( 3,ll) 332141.260 332141.2348(47) 2::: 1
15( 4,12)-14( 4,111 332033.922 332033.9261(473 -4.1 0.5
15( 4,11)-14( 4,101 332033.922 332033.9366(47) -14.6 0.5
15( 5.11)-14( 5,101 331912.413 331912.3942/551 18.8 1
15f 6,10)-14f 6, 91 331765.258 331765.2769[57) -18.9 1
151 7. 9)-14f 7, 8) 331586,392 331586.4117(70f -19.7 1
151 8, 8f-14f 8, 71 331368.679 331368.6508f76) 28.2 1
15( 9, 7)-14g 9, 6) 331101.089 331101‘0911f92f -2.1 1
15[10, 6f-14(10, 5) 330764.324 330764.4117(110~ -87.7 I
15(11, 4)-14(it, 3) 330320.661 330320.5114(235) 149.6 0

16f 0,16)-151 0,151 353931.272 353931.2954(87) -23.4 1

161 1,161-15f 1,151 350551.444 350551.4303(701 13.7 1
16f 1,15)-15f 1,141 357904.209 357904.22~~(71} -13.8 1
16[ 2,15)-15( 2,141 354225.819 354225.8093162) 9.7 1
16( 2,14)-15( 2,13) 354635.040 354635.0528(631 -12.8 1
16( 3,14)-15( 3,131 354278.330 354278.3276(50) 2.4 1
16( 3,13)-15( 3,121 354282.523 354282.5327(51) -9.7 1
16( 4,13)-15( 4,121 354164.718 354164.6904152) 27.6 0.5
16( 4,12)-l!?{ 4,ll) 354164.718 354164.7069(52) 11.1 0.5
16( 5,121-1st 5.111 354033.849 3 54033.8486162 1 .4 1
16( 6,11)-X51 6,101 353876.362 353876.3257(68) 36.3 1
16( 7,10)-15[ 7, 9) 353685.239 353685.2316(86) 7-4 1
16f 8, 9)-15f 8, 8) 353452.826 353452.8265(943 5 1
16( 9, 8)-15( 9. 7) 353167.417 353167.4420(1131 -2&l 1
16110, 7)-15(10, 61 352808.501 3~2808.4690(151) 32.0 1
16111, 6f-15(11, 5) 352335.2922(355)

17( 0,17)-161 0,161 375986.5829(103)

distortion constants have to be considered as fitting parameters which are necessary

if all the measured transitions are to be included in the fit. Similarly large higber-
order centrifugal distortion constants have been found for H&CS (17), H2N-NC (2),
and HNCO (18). In the case of HNCO it could be explained by a resonance between
the ground state and a low-lying excited vibrational state due to centrifugal distortion
coupling (18). Such an interaction is, however, rather unlikely in diazomethane
i~yanamide (2) and thioketene (17).
Therefore the cause of this extreme ~~nt~fu~l disto~ion in H$NN might be
related to the opening of the bond angle HCH in EI&‘NN with increasing rotational
162 SCH;iFER AND WINNEWISSER

TABLE I-Continued

Transf tions Frequencies f MHz ohs.-cal. Weights

JfKa.K,t- J[Ka,Kc) observed calculatedfStd.Dev.1 /kHz Ref.

17( 1.17)-16( 1.161 372438.4726(87)

17( 1;16j-16( 1;15j 380248.7125(87)
17( 2,16)-16( 2,15) 376346.3153(78)
17( 2,15)-16( 2,14) 3?6836.9861(79)
17( 3,15)-16( 3,lQt 376417.9173/58)
17( 3,141-16( 3,131 376423.6230(58)
17( 4,14)-16( 4,13f 376294.5182[59)
17( 4,13)-16( 4,121 376294.5435(59)
17( 5.13)-16( 5.12) 3?6154.1338(73)
17( 6;llj-16i 6,101 375986.0898i85j
17( 7,10)-16( 7, 9) 375782.7079(108)
17( 8, 9)-16( 8, 8) 375535.6341(119)
17( 9, 8)-16( 9, 7) 375232.4270(145)
17110, 81-16f10, 71 374851.1899(216)
17111, 71-16(11. 6) 374348.7977(511)

18( 0,18)-17C 0,171 398030.140 398030.1431(134) -3.1 1

18( 1,18)-17( 1,171 394321.515 394321.5265(108) -11.5 1
18f 1,17)-17( 1,161 402588.708 402588.6573(107) 50.7 1
18( 2,17)-17( 2,16) 398463.413 398463.4412(98) -28.2 1
18( 2,16)-17( 2,15) 399045.5244(99)
18C 3,16)-17( 3,151 398556.912 398556.9098(691 1
18( 3,15)-17( 3,14) 398564.495 398564.5157(691 -220:: 1
18( 4.15)-17( 4.141 398423.368 398423.3504(70) 17.6 0.5
18( 4;14)-17( 4;13) 398423.368 398423.3 884(70) -20.4 0.5
18( 5.14)-17( 5,131 398273.184 398273.1765(88) 7.5 1
18( 6,13)-17( 6,12) 398094.502 398094.4888(108) 13.2 1
18( 7,12)-17( 7,111 397878.7565(137)
18( 8,11)-17( 8,lO) 397616.9878(152)
18( 9,10)-17( 9. 9) 397295.9609(185)
12(11, 2)-ll(11. If 264269.3154(184)

lot 1. 9)-lot 1,101 25305.85 25305.86551270) -15.5 0.1 (151

12( 1,11)-12( 1,12) 35884.29 35884.2921(3581 -2.1 0.1 (15)
13( 1,12)-13( 1,131 41862.15 41862.1204(406) 29.6 0.1 (15)
29( 2,27)-29( 2,281 18674.50 18674.5583(389) -58.3 0.1 (15)
31( 2,29)-31( 2,301 24168.93 24168.99071343) -60.7 0.1 (15)
32( 2,30)-32( 2,311 27316.50 27316.3315(324) 168.5 0.1 (15)
33C 2,311-33( 2.32) 30749.20 30749.1548(338) 45.2 0.1 (15)
35( 2,33 f-35( 2.34) 38526.53 38526.6~78(570) -87.8 0.1 (15)

energies of the rotation about the two-fold symmetry axis of the molecule, thus
changing the force field of the molecule. It is interesting to note that the bond angle
HCH is reported to be 126.1’ (4) considerably larger than the value of 120” appro-
priate to pure sp’ hyb~~~ation at the carbon atom, a value almost approached in
keten (OHCN = 122.6’ in H&CO). Recently Jensen et al. (19) reported the equi-
librium structure for the methylene radical, CHz, in the X3& ground state. The bond
angle for CH;! was found to be 133.88”, which puts diazomethane indeed between
the limiting cases of pure $8 hybridization as in ethylene and the methylene radical.
Walch and Goddard (20) pointed out in their generalized valence bond description
of the low-lying electronic states of ~~omethane that the ground electronic state is
best described as a singlet biradical-like state
H,
,c-sIJ=N:.
H
 ROTATIONAL SPECTRUM OF DIAZOMETHANE 163

TABLE II

Rotationat and Centrikgal DistortionConstantsof Diazomethanefor Watson’s

S-Reduced Hamiltonianin I’-Axis Representation

A/MHz 272 979.1(8.1)

B/MHz 11 305.42697(45)

C/MHZ 10 845.22028(47)

DJ/kHZ 4.14620(74)

D&kHz 396.817(92)

%/MHz 22.0 (fixed)=)

dl,'kHz -192.55(42)

d2/Sz -57.27(39)

H&'Hz 2.081(42)

HKJ/Hz -492.4(8.3)

L&Hz 1.26(301
2.085(56) x 10-4
SJK/Rz
-2
S&Hz -3.41(49) x 10
-4
T&HZ -2.57(38) x 10
-6
D&HZ -1.62(11) x 10

A = ~,-~a-~,,amuX~ 0.0456')

Number of data: 142

Standard deviation of fit: 25.0 kHz

a)D~ value according to Moore 191

bl(BxI) = 5.053790(141x105 MHzamdi2 (24)

Thus, in order to complete the centrifugal distortion and structural analysis, rovi-
brational infrared data would have to be included in the analysis of the various isotopic
species of diazomethane.
Since H&LYNNcan formally be considered the addition product of methylene, H2C,
to N2, its presence in interstellar dust clouds cannot be ruled out. Indeed the recom-
bination of CH2 and N2 to give H2CNN has been observed in an Nz matrix
at liquid He temperatures (21). Using the kinetics data of Braun et al. (22) of
N&H2Nz mixtures following flash excitation, Lat&er and Okabe (23) give an acti-
vation energy of 53 kcal/mol for the recombination reaction CH2 + N2 - H$XN,
while Moore and Pimentel (21) conclude that the formation of diazirine from CH2
and N2 has a much higher activation energy. This finding is consistent with the
theoretical considerations of Walch and Goddard (20).
164 SCHAFER AND WINNEWISSER

The authors would like to express their thanks to Dr. Brenda P. Winnewisser for many helpful discussions
and critically reading and commenting on the manuscript. The experimental work was in part supported
by funds from the Deutsche Forschungsgemeinschaft, the Fends der Chemischen Industrie, the Max-Planck-
Institut for Radioastronomie through the grants of Dr. Gisbert Winnewisser, and the Justus-Liebig Uni-
versitit Giessen. All calculations were carried out at the Hochschulrechenaemrum of the Justus-Liebig-
Universitit, a service which is greatly acknowledged. The secretarial help of the National Research Council
of Canada is greatly appreciated. We express our sincere thanks to Dr. Peter Cox of Bristol University for
his courtesy to make part of his diaxomethane data available to us prior to publication.

Note added in proof: The centrifu8aldistortion resonance coupling scheme (18) can be used in quali-
tatively explaining the large centrifugal distortion effects according to some mnt calculations of K. Ya-
mada. For a quantitative proof, high resolution ir data are necessary.

RECEIVED: August 12, 1982

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