Vibration rotation bands of 15N218Odetermination of precise values of internuclear distances

JOURNAL OF MOLECULAR SPECTROSCOPY 25, 3 4 - 6 1

(1968)

Vibration Rotation Bands of

,~2

Determination of Precise Values of Internuclear Distances JAMES L. G~IGGS, JR.,* AND ]~(. NA~A]~A]~ RAO Laboratory of Molecular Spectroscopy and Infrared Studies, Department of Physics, The Ohio State University, Columbus, Ohio 43210 AND L. I-I. JoNEs AND R . M . POTTER Los A lamos Scientific Laboratory, Los Alamos, New Mexico 87544 The rotational structure of sixteen vibration rotation .bands of the 15N~80 molecule in the 2-5 tt region has been measured and analyzed. Since the molecule 15N~sO is the heaviest of all the stable isotopic species of nitrous oxide, the study of its infrared bands allowed the determination of very accurate values for the equilibrium internuclear distances r~--N = 1.12665 ± 0.0005 A and r~--o = 1.1856~ ± 0.0005 A. The distance between the end atoms is determined with a much higher precision (rN--~ -k rN--O) = 2.31230 ± 0.00003 A. INTRODUCTION T h e n i t r o u s oxide molecule offers t h e p o s s i b i l i t y of t w e l v e stable isotopic species, f o r m e d f r o m c o m b i n a t i o n s of t h e isotopes I~N, I~N, ~O, ~70, a n d ~SO. Since t h e o r d i n a r y species 1~N~60 is t h e l i g h t e s t of these, while t h e species ~N~80 is t h e heaviest, t h e m o l e c u l a r c o n s t a n t s o b t a i n e d f r o m t h e s e t w o p a r t i c u l a r species should f o r m a n i m p o r t a n t basis for d e t e r m i n a t i o n of precise v a l u e s for t h e i n t e r n u c l e a r d i s t a n c e s a n d a discussion of t h e p o t e n t i a l e n e r g y functio~l of t h e n i t r o u s oxide molecule. T h e p r e s e n t article r e l a t e s to t h e i n t e r n u c l e a r dist a n c e s in t h e n i t r o u s oxide molecule. C h e m i c a l s y n t h e s i s of a d e q u a t e a m o u n t s of ~SN~sO gas n e e d e d for s t u d y i n g t h e v i b r a t i o n r o t a t i o n a b s o r p t i o n b a n d s in t h e i n f r a r e d was u n d e r t a k e n a f t e r t h e v3 Supported, in part, by the U. S. Atomic Energy Commission (COO-882-13) through a contract with The Ohio State University Research Foundation as a joint project between the Laboratory of Molecular Spectroscopy and Infrared Studies at The Ohio State University Physics Department and the Los Alamos Scientific Laboratory, Los Alamos, New Mexico. * Present address: Department of Physics, U. S. Air Force Academy, Colorado 80840; Major James L. Griggs, Jr., participated as a student under the AFIT program. 34

INFI~ARED BANDS OF ~N~sO

2500

3000

3500

4000

35

4500 cm -I

WAVE NUMBER

Fro. 1. Over-all picture of bands of 1 5 N~18 O in the region 2400-4600 em

i

o

I tIJ

,

o

o~-oo°ol ~,°1 f ! I 4,51

I I 4;O I I I I 45 I I I I SO V I I ,r 25 I kA,

[

2~ I I I ] q)

52'?0cm -~

5260 ~m -~

05~10fO ~1]~ r55is it~ f--{- 'r3dt-",-',-Jv~ O tz70~

; ,.-' ,.J ~d r ~ r j ,.' ~' f5

I

i

o2%oo°oi 5 I I I I 1~ I I ] I ~ I I I I R';o> u,(1) lA_l 52'50 cm-' os'vofo ~--%? / ? 10 r'

02°1-00a01 I ,I 1:51 o5'1ofol

/ I I @ I I I RI1) (~

,s I J I I lo 5240 c~ ~

!

_U,~I I @ I ~ 2

I I I ~°~ I I 12~ I 5250 cm-' '

I I

Id-Y~Y~ 52'20

I r' r' ~s r' r' r' ," ~o ,.' ,.' ,' ,,~S ,.F,.,22

c m -1

i::::' , ~

o

o2~-oo°o~5 I I [ I ~;o I_1

I I 4;s t 52'10 cm-'

Fro. 2. Rotational structure of bands meter and gas pressure--10 em of I{g.

I

I '

--go-]

q ~ S 52'00 c~n '

of ~SN~O aS 3.1-~ region;

absorption

pat, lt

-one

fundamental of this species was identified (1) by analysis of an extraneous band observed during the infrared absorption studies of 15N'80 (2). The natural abundance of the isotopic molecule 15N~80, estimated as equal to the product of the individual atomic abundances, is only about 1 part in 36 million parts of natural nitrous oxide.

GRIGGS, ET AL.

36

TABLE I

MOLECb-LAR

CONSTANTS(a) OF 15N2180 OBTAINED FROM BANDS W I T H GROUND STATE AS L O W E R STATE

UPPER STATE

Yo

BO000

(Bt-B0000)

D0000

(Dr-Do000)

(Hi-H0000)

x 107

x 109

x i0 I0

x 1013

- 167 i 13

---

2001

4541.9597 i 12

0.38192

+

3

- 58938 ±

30

165 ±

9

0002

4266.9827 ±

0.38184

±

2

- 60580 ±

7

146 ±

6

8

---

3000

3664°9966 ± 12

0°38184

±

3

- 39264 ±

30

141 ±

9

- 435 ± 15

2200

3587.7186 ± i0

0.38190

±

3

- 23867 ±

40

179 ± 21

507 ± 38

i001

3347.3907 ± ii

0°38185

±

2

- 45343 ±

17

143 ±

0201

3246.0213 + i0

0.38181

i

3

- 22013 ±

36

143 ± 20

2702.004

0.38170

± ii

- 28385 i

44

108 ± 36

011el 011dl

±

4

(2702o03)(c)

---

(- 21998 ± 117)

5

9

0.38188

±

2

- 28423 ±

17

143 ±

4

0001

2147.5881 ± i0

0.38186

±

2

- 30243 ±

6

142 ±

5

I000 (e)

1225o984

.

14821 ±

47

5

(a)values in cm-lo

.

.

0.381862 ±

.

8

---

.

.

145 ±

5

--15 i 8(b)

. . . . . . (- 105 ± 37)

2447.1818 ±

±

56 ±

514 i 32

---

2000 (d)

AVo for 0000 state

-

--23 ± 9 (b)

- 186 ±

---

6

---

. . . . . . .

.

2

.

.

.

.

.

. . . . . .

Standard deviations are quoted in units of the last significant

figure° (b)Although the effect of f~H is seen, no significant value could be determined for HO000 from the present data; in fact, the computations led to values for HO000 of (i ± 4) x 10 -12 cm -I for the (2v I + v3) band and (7 i 4) x 10 -12 cm -I for the (2v I + 2v2) band.

It appears that

H0000 has the same order of magnitude as in 14N2160 , namely I x 10 "12 cm'l. (e)Parentheses signify that insufficient data resulted in lack of precision for the constants of this level; structure in the Q branch could not be m e a s u r e d to high enough J values. (d)Measurements of 15N2160 impurity band lines (vide Table 17

) led to the constants

v ° = 2523°2534 ! 15; B ~ = 0°40487 ± 5; B t - B ~ = (-3370 ± 4) x 10-6; D t = D H = (12 i 3) ~ !0 -8, e)From preliminary measurements.

EXPERIMENTAL DETAILS OBSERVATION AND MEASUREMENT OF BANDS

Figure i displays an over-all picture of the near infrared bands of 15N~80 observed with a high resolution vacuum spectrograph. Reproduction of one of the high resolution scans of the bands at 3.1 ~ is presented in Fig. 2; this region shows the (2~2 q- vs) band and its associated "hot" band (3,2 -t- ,3 - ,2). The g-type doubling can be seen clearly in the "hot" band. Most of the combination bands studied in this work show the presence of the "hot" bands from the 0110 level. Pictures of all the 1~N~80 bands recorded thus far have been included in a dissertation by Griggs (3) along with details of calculations made.

INFRARED BANDS OF 15N2~80

37

TABLE II

MOLECULAR CONSTANTS (a) OF 15N2180 OBTAINED FROM "HOT" BANDS WITH 0110 AS LOWER STATE

!

DI

(B -BOII0) UPPER STATE

Yo

2111

4543.5939 ± 24

0.38249

0112

4240.6497 ± Ii

0.38232

2310

3586.866(b)

B0110

D0110

x 106 ±

8

± .

- 6002 ± .

.

.

.

.

.

.

(q -q0110 )

x 105

---

70 ± 14

133 ± 16 .

q0110

x 109

368 ± 98

2 .

I -D0110)

x 109

- 5647 ± 13

3 .

(

x 107 2677 ± 94

. . . . . . . . . .

.

.

.

.

.

iiii

3341o3482 ± 13

0.38229

±

4

- 4391 ±

4

114 ± 22

8 ± 3

67 ±

4

1021 ± 21

0311

3225o1704 ± I0

0°38224

±

3

- 2328 ±

4

106 ± 14

23 ± 3

65 ±

2

5585 ± 12

2110

2461.8315 ± 23

0.38243

±

6

- 2619 ±

9

152 ± 33

- ii ± 7

72 ±

6

2980 ± 36

0111

2134.4126 ± 14

0°38230

±

4

- 2991.±

2

92 ± 15

Av. for 0110 state (c)

0°382301 ± 16

(a)values in cm-lo figure°

---

114 ±

8

-

.

. . . . . . . . . ---

66 ±

2

---

Standard deviations are quoted in units of the last significant

(b)Band center derived from a fragmentary set of observational data. (C)The band origin for the y band has been deduced to be 567.591 cm -I by applying Ritz combination to the (v 2 + v3) ~nd (v 2 + v 3 - v2) bands°

Spectral positions were determined relative to the 1-0 and 2-0 band lines of CO, HC1, and DC1 molecules (4, 5) following the "single-pen technique" described by Rao, Itumphreys, and Rank (4). The "standards" were recorded at regular intervals during spectral scans by rotating the foreprism monochromator for changing the grating order and interchanging the absorption cell containing 15~TIB~ " t " = t) wl n cells of CO, HC1, or DO1. Data reduction and evaluation of rotational constants was done by using a least squares polynomial curve fitting program written for an IBM 7094 digital computer as in the case of the 15N180spectra (2). MOLECULAR

CONSTANTS

]~otational constants and band origins determined from the bands observed by absorption from the ground state are collected in Table I. Similar constants pertaining to the "hot" bands are included in Table II. A complete discussion of the effect of Fermi resonance in the 15~,N 218 0 spectra will be presented after more bands are observed and analyzed. The Fermi diad 10°1 and 02°1 has been studied in this investigation. Following the procedure outlined by Rao and Nielsen (6), a preliminary value of 32.8 cm-I was evaluated for the third order term lq22 in the potential energy function.

38

GLIGG8, ET AL.

-I TABLE Ill

OBSERVED

AND CALCULATEO

WAVE NUMBERS

0 OF T H E

ROTATIONAL

STRUCTURE

OF

THE 2 0

(V&C.CM.

0 1~00

15 0 BAND

OF

)

18 N

Q. 2

............................................................ ............................................................

J RIJ)OBS RIJ)CALC O-C PIJ)OBS PIJ)CALC ~-C XIO0 XIO0 ............................................................ 0 I 2 3 4 B 6 7 8 9 i0 ii 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 33 31 52 55 34 35 36 37 38 39 48 41 42 43 44 45 46 47 4S 49 50 51 52 53 54

4542.721 4548.460 4544.181 4544.892 4545.602 4846.303 4546.987 4547.683 4548.301 4548.945 4549.584 4580.2[2 4550.885 4851.419 4551.994 4552.569 4853.133 4553.694 4554.238 4554.772 4555,280 4555.777 4556.266 4556.744 4557.215 4557.675 4558.129 4558.561 4558.985 4559.394 4559.788 4560.163 4560.544 4560.908 4D61.258 4D61.598 4561.933 456~.261 4562.564 4562.855 4563.136 4563.413 4563.675 4563.897 4uh4.142 4564.569 4564.579 4564.779 4564.971 4565.[60

4542.712 4543.452 4544.180 4544.897 4545.602 4846.295 4546.976 4547.646 4548.303 4548.949 4549.583 4550.206 4850.816 4551.415 4552.002 4552.577 4553.140 4553.69[ 4854.23[ 4554.759 4555.275 4585.779 4556.272 4586.752 4557.221 4557.679 4558.124 4558.558 4558.980 4559.390 4559.789 4560.176 4560.551 4560.914 4561.266 4561.606 4561.935 4562.251 4562.557 4562.850 4563.132 4563.402 4563.661 4563.908 4564.144 4564.368 4564.5U0 4564.781 4564.971 4565.148 4565.315 4565.470

0.9 O.B 0.0 -0.5 -O.i 0.7 l.G 0.7 -0.3 -0.4 O.C 0.6 0.9 0.4 -0.7 -0.8 -0.7 0.8 0.7 1.3 0.5 -0.2 -0.6 -0.8 -O.b -0.6 0.5 J.3 0.5 0.5 -0.i -i.5 -0.7 -0.6 -0.8 -0.8 -0.2 0.9 0.7 0,3 0.4 1.0 1.4 -i.i -0.2 0.I -0.I -0.2 0.6 I.i

454L.I97 4540.427 4539.644 4538.838 4538.015 4837.190 4536.358 4536,52[ 4554.660 4855.785 4532,998 4532,022 4551.113 4550.187 4529.261 4528.331 4527.378 4526.405 6525,431 4524.454 4828.45~ 4522,436 4521.418 4520.394 4519.341 4518.283 4517.224 4516.145 4515.041 4513.947 4512.839 4911.705 4516.569 4509.482 4508.261 4507.091 4505.918 4504.720 4503.510 4502.506 4501.072 4499.827 449~.588 4497.5[9 4496.~47 4494.771 4493.456 449~.157 4490.846 4489.489 4488.158 4486.820 44~5.442

4541.196 4540.420 4539.633 4838.834 4538.023 4537.200 4836.366 4535.5[9 4554.661 4533.792 4552;910 4532.617 4531.112 4530.196 4529.267 4528.327 4527.576 4526.415 4525.438 4524.451 4523.455 4922.445 4521.422 4520.588 4519.344 4518.28B 4517.28U 4516.141 4515.05~> 4513.947 4512.854 4511.708 4510.572 4509.425 4508.264 4507.095 4505.910 4504.716 4503.511 4502.295 4501.067 4499.828 4498.577 4497.316 4496.043 4494.7D9 4493.465 4492.157 4490.839 4489.511 4488.171 4486.82u 4485.458 4484.085

V.I v.7 I.l U.4 -~.5 -[.0 -~.7 ~.2 -u.2 -~.9 -~,.8 5.5 .I -0.9 -u.6 6.4 V.3 -J.7 -i.7 0.3 -0.0 -1.7 -~.3 L.5 -~.3 -:.5 ~.4 J.2 -~,.9 -u,O u.6 -~,.6 -[.2 5.9 -J.3 -.2 i.8 ~.3 -~,i l.l 6.5 -~.0 1.0 0.3 .4 1.2 --~.7 $.0 ~.7 -2.2 -1.3 .0 -i.~

INFI%AI%ED BANDS OF

T6~LE

IV

OBSERVED

AND

CALCULATED

OF THE R O T A T I O N A L STRUCTURE OF

[HE

21

15

18 N20

WAVE

NUMBERS

I

i 1-01

30

-I (VAC.CM. ) 15

0 ~ANO OF

18 N

O. 2

............................................................ ............................................................ J R(JIOBS R[J)CALC 0-0 P(J)OBS P(J)CALC U-C XlO0 x[O0 ............................................................

0 I 2 3 4 5 6 7 8 9 I0 II 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 54 55

4545.812 4546.540 454T.261 4547.956 4548.633 4549.306 4549.977 4550.641 4551.265

4556.513

4545.096 4545.827 4546.547 4547.255 4547.952 4548.638 4549.312 4549.975 4550.627 4551.267 4551o896 4552.513 4553.119 4553.714 4554.297 4554.869 4555.429 4555.978 4556.516

-1.5 -0.7 0.6 0.4 -0.5 -0.6 0.2 1.4 -0.2

-0.2

45B2.77~ 4531.87~ 4530.947 4530.004 4529.068 4528.110 4527.I41 4526.170 4525.175 4524.186 4523.145 4522.141 4521.109 4520.064 4519.002 4517.940 4516.871 451b.780 4514.671 4515.572 4512.443 4511,311

4542.058 4541.271 4540.472 4539.662 4538.841 4538.008 4537.164 453b.309 4535°440 4534.565 4533.677 4532.777 4531.866 ~530.944 4530.010 e529.066 452~.iI0 4527..44 4526.166 4525.177 4524.176 4523.165 4522.14B 4521.109 4520.005 4519.009 4517.943 4~16.865 4515.777 4514.677 4515.566 4512.444 4511.312 4510.168

0.1 i.I J.4 -~.6 9.2 -i.l -~.2 ~°4 -e.2 0.9 -2.0 --.2 -~.[ -~.I -+.7 -~.3 L~°6 ~.4 -~.6 ~.6 -,).i -.[,

40

GRIGGS, ET AL.

TABLE V

OBSERVED

AND CALCULATEO

WAVE N U M 8 E R S 0

OF f H £

ROTATIONAL

STRUCTURE

OF I H E

O0

-I (VAC.CM.

0 2-00

15 0 ~&NO OF

L8 N

O. 2

............................................................ ............................................................ J R(J)OBS R(J)CALC O-C P(J)085 PIJ)CALC [)-C XlO0 XIO0 ............................................................ 0 I 2 3 4 5 6 7 8 9 I0 ii 12 13 14 15 16 17 i8 19 20 21 22 25 24 25 26 27 28 29 30 31 32 33 34 35 36 37 88 39 40 41 42 48 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58

4267.735 4268.48I 4269°209 4269.917 4270.615 4271.307 4271.990 4272.660 4273.319 42?3.953 4274.585 4275.195 4275.802 4276.404 4276.989 4277.557 4278.i07 4278.650 4279.i8I 4279.702 4280.218 4280.715 4281.202 4281.673 4282.128 4282.570 4283.005 4283.427 4283.840 4284.243 4284.630 4285.009 4285.568 4285.719 4286.056 4286.375 4286.685 4286.983 4287.276 4287.552 4287.816 4288.071 4288.317 4288,544 4288.759 4288.954 4289.149 4289.341 4289,647 4289,787

4267.734 4268.474 4269.201 4269.916 4270.619 4271.310 4271.989 4272.656 4273.310 4273.952 4274.583 4275.201 4275.807 4276.400 4276.982 4277.551 4278.108 4278.654 4279.186 4279.707 4280.216 4280.712 4281.196 4281.668 4282.128 4282.575 4283.010 4283.434 4283.844 4284.243 4284,680 4285,004 4285.366 4285.716 4286.053 4286,378 4286,691 4286.992 4287.281 4287,557 4287.821 4288.073 4288.512 4288.540 4288.755 4288.958 4289.148 4289.326 4289.492 4289.646 4289.787 4289.916 4290.038 4290.137

0.0 0.8 0.8 0.0 -0.~ -0.3 0.I 0.5 0.9 0.0 0.3 -0.6 -0.4 0.3 0.7 0.5 -O.i -0.4 -0.6 -0.5 0.2 0.3 0.6 0.5 0.0 -0.5 -0.5 -0.7 -0.5 -0.i 0.I 0.5 0.2 0.3 0.2 -0.4 -0.6 -0.9 -0.5 -0.5 -0.5 -0.2 0.4 0.4 0.5 -0.3 0.1 1.4 0.2 0.~

4266.219 4265.447 4264.663 4263.853 4263.030 4262.213 4261.386 4266.534 4259.671 4258.792 4257.923 425T.027 4256.115 4255.184 4254.256 4253.321 4252.358 4251.380 4250.401 4249.420 4248.405 4247.382 4246.350 4245.321 4244.27i 4243.193 4242.122 4241.038 4239.930 4238.815 4237.695 4286.857 4239.490 4254.285 4233.078 4231.884 4230.685 4229.487 4228.257 4227.005 4225.784 4224.522 4223.245 4221.980 4226.678 4219.367 4218.054 4216.725 4215.372 4214.057 4212.665 4211.800 4209.906 4208.487 4207.090

4202.768

4266.219 4265.443 4264.655 4263.855 4263.043 4262.219 4261.383 4260.534 4259.674 4258.801 4257.917 4257.020 4256.111 4255.190 4254.25? 4253.312 4252.355 4251.386 4250.405 4249.412 4248.407 4247.389 4246.360 4245.319 4244.265 4243.200 4242.122 4241.033 4239.931 4238.818 4237.692 4236.555 6235.405 4234.244 4233.070 4231.885 4230.687 4229.478 4228.256 4227.023 4225.777 4224.520 4223.250 4221.969 4220.676 4219.371 4218.053 4216.724 4215.383 4214.030 4212.665 4211.288 4209.899 4208.498 4207.086 4205.661 4204.224 4202.776

-0.0 J.3 0.8 -J.2 -0.8 -J.7 ~.3 -6.i -~.3 -6.9 ~.7 J.7 ~.3 -~.6 -~.2 0.8 J.3 -J.6 -].4 J.8 -O.O -6.8 -i.0 r.2 ~.6 -5.7 -0.0 u.5 -0.2 -;.3 ~.3 0.2 -0.5 -£.8 6.8 -].I -~.2 0.9 0.1 -1.8 u.7 0.2 -0.5 l.l ~.2 -~.4 ~.I O.O --i.1 .Z --L.O 1.2 ~.7 -1.2 ~.4

-0.8

INFRARED

TABLE

OF T H E

V[

OBSERVED

ROTA[IONAL

B A N D S OF 15N~80

~NO CALCULATED

S[RUCTURE

U~

[HE Ol

WAVE

NUMBERS

1

I 2-01

41

-I (VAC.CM. } i~

0 ~ANO

OF

18 N

O. 2

............................................................ ............................................................ J R(J)OBS R(J)CALC O-C PIJ)OBS P(J)CALC D-C XIOC XIOO ............................................................ 0 I 4242.149 2 4242.869 4242.~78 -0.8 4239.114 3 4243.590 4243.594 -0.4 4238.322 4238.326 -C.3 4 4244.299 4237.536 4237.525 i.l 5 4244.994 4244,99[ 0.2 4236.713 4236.7[2 J.l 6 4245.670 4245.672 -0.2 4255.883 4235.888 -3.5 7 4246,340 4235.047 4235.051 -0.4 8 4246.997 4246.997 -O.C 4254.203 9 4247.635 4247.641 -0.6 4233.350 4233.342 0.8 4248.274 -O.O 4232.473 4232.470 ~.4 IO 4248.274 I[ 4248.899 4248.894 0.4 4251.581 4231.585 -U.4 12 4249.503 4230.689 13 4250.097 4250.099 -0.2 4229.784 4229.780 U.4 14 4250.675 4250.683 -0.8 4228.864 4228.860 5.4 15 4251.255 4251.255 -0.2 4227.924 4227.927 -3.3 16 4251.814 4251.815 -0.2 4226.985 4226.027 $.3 17 4252.364 4226.030 18 4252.908 4252.900 0.8 4225°062 4225.059 3.4 19 4255.424 4224.075 4224.078 -0.3 20 4253.937 4253.935 0.I 4223.084 4223.08b --0.2 4222.082 0.9 21 4254.429 4254.435 -0.@ 4222.091 22 4254.922 4254.923 -0.I 4221.066 4221.066 -O.O 25 4255.38g 4255.399 -I.0 4220.033 4220.058 -U.5 24 4255.866 4255.862 0.5 4218.995 4218.998 -(.4 25 4256.316 4256.314 0.2 4217.956 4217.947 I.¢ 26 4256.761 4256.?53 0.7 4216.883 4216.883 -0.0 27 4257.188 4257.181 0.7 4215.799 4215.807 -0.8 28 4257.602 425?.596 0.6 4214.725 4214.720 0.3 29 4257.999 4213.623 4213.620 <,,3 30 4258.388 4258.390 -O.B 4212.505 4212.509 -~,.4 31 4258.769 4211.372 4211.386 -1.4 32 4259.133 4259.136 -0.3 4210.261 4210.25C i.I 33 4259.490 4259.491 -0.0 4209.092 4209.103 -[.2 34 4259.841 4259.833 0.8 4207.947 4207.944 C.2 35 4260.170 4280.164 0.6 4206.779 4206.774 0.5 36 4260.482 4205.591 37 4260.7g0 4260.788 0.i 4204.598 4204.396 0.2 38 4261.083 4203.189 4203.190 -J.[ 39 4261.365 4201.970 4201.971 -0,I 40 4261~630 4261.634 -0.5 4200.741 41 426i.881 4261.892 -I.I 4199.499 42 4262.138 4198.245 43 4262.371 44 4262.591 4262.593 -0.2

42

GRIGGS, ET AL.

TABLE V I I

OBSERVED AND C A L C U L A T E D WAVE NUMBERS

0 OF THE R O T A T I O N A L STRUCTURE OF THE 30

-i (VAC.CM.

0 0-00

15 0 BAND OF

)

18 N

0, 2

............................................................ ............................................................

J R|J)OBS R(J)CALC O-C P|J]OBS P[J)CALC O-C Xl00 XI00 ............................................................ 0 1

2 3 4 5 6 7 8 9 I0 II 12 13 14 15 16 17 18 19

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50

3665.762 3666.497 3667.236 3667.978

3669.416 3670.117 3671.524 3672.207 3672.875 3673.546

3675.509 3676.137 3676.78? 3677.419 3678.021 3678.618 3679.221 3679.816 3680.403 3680.986 3681.546 3682.102 3682.661 3683.214 3683.751 3684.276 3684.794 3685,314 3685.824 3686.332 3686.827 3687.311 3687.784 3688.258 3688.720 3689.186 3689.637 3690.079 3690.525 3690.936 3691.789 3692.204 3692.597 3692.997

3665.752 3666.500 3667.241 3667.973 3668.697 3669.414 3670.123 3670.823 3671.516 3672.202 3672.879 3673.548 3674.210 3674,864 3675.510 36T6.149 3676.779 3677.402 3678.017 3678.625 3679.224 3679.816 3680.401 3680.977 3681.546 3682.108 3682.662 3683.208 3683.747 3684.278 3684.802 3685.319 3685.828 3686.329 3686.824 3687.311 3687.790 3688.263 3688.728 3689.186 3689.637 3690.081 3690.518 3690.947 3691.370 3691.786 3692.195 3692.597 3692.993 3693.382 3693.763

1.0 -0.4 -0.5 0.5

0.3 --0.6 0.7 0.5 -0.4 -0.3

-0.I -1.2 0.8 1.6 0.4 -0.7 -0.3 -0.I 0.2 0.8 -0. I -0.6 -0.I 0.6 0.4 -0.2 -0.8 -0.5 -0.4 0.3 0.4 0.0 -0.6 -0.5 -0.8 0=0 0.0 -0.1 O.B -1.2 0.2 0.9 -0.0 0.4

3664.230 3663.465 3662.687 3661.890 3661.088 3660.301 3659.490 3658.659 3657.838 3657.009 3656.171 3655.310 3654.463 3653.595 3652.713 3651.842 3650.955 3650.048 3649.155 3648.246 3647.317

3645.471 3644.521 3643.577 3642.613 3641.648 3640.683 3639.711 3638.715 3637.728 3636.727 3635.712 3634.707 3633.677 3632.648 3631.622 3630.571

3627.397 3626.336 3625.264 3624.163 3623.089 3621.972

3618.645

3664.233 3663.461 3662.682 3661.B95 3661.100 3660.297 3659.486 3658.668 3657.841 3657.007 3656.165 3655.316 3654.458 3653.593 3652.721 3651.840 3650.952 3650.056 3649.153 3648.242 3647.323 3646.397 3645.463 3644.522 3643.573 3642.617 3641.653 3640.682 3639.704 3638.718 3637.725 3636.725 3635.717 3634.703 3633.681 3632.652 3631.616 3630.573 3629.523 3628.466 3627.402 3626.331 3625.254 3624.170 3623.079 3621.981 5620.877 3619.766 3618.648 3617.525

-5.3 u.3 0.5 -~.5 -I.I 0.4 0.4 -0.9 -;,.3 0.2 0.6 -0.6 (;.5 0.2 -©.8 0.2 ~.3 -0.8 3.2 (!.4 -0.6

0.8 -0.I i3.4 -0.4 -0.6 0.0 0.7 -0.3 0.3 0.2 -u.5 0.4 -0.4 -0.4 0.6 -0.2

-0.5 0.5 1.0 -~.7 1.0 -0.9

-0.3

INFRA12ED BANDS OF

TABLE V I I I

OF

THE

OBSERVED

ROTATIONAL

AND CALCULATED

STRUCTURE

OF

THE

15

N 2180

WAVE NUMBERS

2200__0000

BAND

43

-I (VAC.CM.

OF

15

18

N

O.

2 ............................................................ ............................................................ J RIJ)OBS R[J)CALC 0-C P(J)OBS P(J}CALC U-C XlOu XlO0 ............................................................ 0 I 2 3 4 5 6 7 8 9 I0 ii 12 13 14 [B 16 17 18 19 20 21 22 23 24 25 26 27 28 29 50 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56

3589.233 3589.977 3590.733 5591.467 3592.194 5592.928 3593.658 3594.382 3595.088 3595.804 3596.511 3597.206 5597.908 3598.598 3599.287 3599.971 3600.639 5601.317 3601.984 3602.639 3603.292 3603.949 3604.594 5605.232 5605.863 3606.495 3607.124 3607.734 3608.342 3608.958 5609.564 3610.164 3610.749 361[.335 3611.926 3613.063 3615.624 3614.188

3615.828 3616.370 3616.894 3617.424 3blfl.458 5618.956

3620.436 3621.387 3621.856 3622.332

3588.478 358g.232 3589.981 3590.726 3591.466 3592.201 3592.931 3593.657 3594.377 3595.093 3595.803 3596.509 3597.210 3597.906 3598.598 5599.284 3599.965 3600.641 3601.312 3601.978 3602.639 3603.294 3603.945 3604.590 3605.231 3605.866 3606.495 3607.120 3607.739 3608.353 3608.961 3609.564 3610.161 3610.753 3611.340 3611.921 3612.496 3613.066 3613.630 3614.188 3614.741 3615.288 3615.829 3616.365 3616.894 3617.418 3617.936 3618.447 3618.953 3619.453 3619.947 3620.435 3620.917 3621.393 3621.863 3622.326 3622.784

0.2 -0.4 0.7 0.i -0.7 -0.3 0.2 0.5 -0.4 O.O 0.2 -0.5 0.i 0.I 0.4 0.6 -0.2 0.5 0.6 0.1 -0.2 0.4 0.4 0.I -0.3 -0.I 0.4 -0.5 -I.0 -0.3 -0.0 0.2 --0.5 -0.5 0.6 -0.3 -0.6 -0.0

-0.i 0.5 0.0 0.6 1.0 0.3

0.i -0.6 -0.7 0.5

3586.193 3585.412 3584.631 3583.853 3583.066 3582.265 3581.469 3580.674 3579.861 3579.053 3578.240 5577.411 3576.589 3575.764 3574.926 3574.084 3573.245 3572.387 35Z[.532 357G.677 3569.805 3568.937 3568.069 3567.181 5566.309 356b.417 3564.514 3563.614 3562.710 3561.793 3560.890 3559.963 3559.036 3558.108 3556.228 3555.282 3554.325 3553.373 3552.403 3551.436 3549.481 3548.502 3547.499 3546.517 3544.498 3543.491 3542.465 3541.447 3540.414

3586.955 3586.186 3585.413 3584.635 3583.852 3583.064 3582.272 3581.475 3580.673 3579.866 3579.055 3578.238 3577.417 3576o591 3575.761 3574.925 35?4°085 3573.239 3572.389 3571.554 3570.674 3569.809 3568.939 3568.064 3567.185 3566.300 3565.410 3564.515 3563.615 3562.710 3561.799 3560.884 3559.963 3559.037 3558.106 3557.170 3556.228 3555.281 3554.328 3553.370 3552.407 3551.438 3550.464 3549.484 3548.499 3547.508 3546.511 3545.509 3544.501 3543.487 3542.468 3541.443 3540.412 3539.375 3538.353 3537.286

D.7 -~.I -0.4 0.I %.2 -4.7 -0.5 2.1 -0.5 -u.2 J.2 -0.6 -9.2 O.3 ~,I -3.I 5.6 -0.2 -0.2 L.3 -~.5 -d.5 C.5 -J.4 1.0 ~.7 -O.l -J.l ~.0 -~.6 ~.6 --0.0 -J.2 0.2 -J.O ~.I -0.3 0.3 -0.4 -0.3 -v.3 b.3 -(].8 0.6 -0.3 0.4 -9.3 J.4 ~.2

GRIGGS, ET AL.

44 T A B L E %X

OF

THE

OBSERVED

ROTATIONAL

AND CALCULAIEO

STRUCTURE

OF

THE

10

WAVE

NUMBERS

0

0 1-00

-1 {VAC.CM. ) 15

0

~ANO

OF

18 N

O. 2

............................................................ ............................................................ J

R(J)OBS

R(JICALC

O-C

"

P{J)QBS

P(J)CALC

(i-C XIO0

3346.627 3345.854 3345.072 3344.281 3343.482 3342.673 3341.855 3341.027 3340.191 3339.3%6 3358.492 3337.629 3336.757 3335.87b 3334.985 3334.086 3333.178 3332.260 3331.334 3330.399 3329.455 3328.502 3327.540 3326.569 3325.589 3324.600 3323.602 3322.595 3321.579 3320.555 3319.521 3318.479 3317.427 3316.367 3315.298 3314.220 3313.133 3312.037 3310.933 3309.819 3308.697 3307.566 3306.426 3305.278 3304.120 330?.954 3301.779 3300.595 3299.403 3298.?02 3296.992 3295.773 3294.546 3293.3[0 3292.065 3290.811 3289.549 3288.278 3286.999 3285.711 3284.414 3283.109 3281.795 3280.472 3279.141 3277.802 3276.453 3275.097

0.i -©.6 -i.7 1.7 -¢.3 -3.7 o.i G.5 -~J.3 -6.2 0.6 -O.O -3.8 -J.9 O.3 0.9 0.0 0.5 -0.I -0.1 0.6 -0.6 0.3 5.5 -0.2 0.I 0.2 -0.5 -u.5 [.6 -b.l U.4 0.I -0.3 0.4 -C.6 -0.i u.l -0.6 0.4 -0.5 0.2 O.l -C.2 0.6 -1.4 I.I

X[00 ............................................................

0 1 2 3 4 5 6 7 B 9 I0 Ii 12 [3 14 15 16 17 18 19 ZO 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68

3348.139 3348.888 3349.629 3350,361 3351.093 3351.770 3352.475 3353.176 3353.858 3354.523 3355=ig0 3355.857 3356.502 3357.123 3357.748 3358.377 3358.989 3359.590 3360.166 5360.751 3361.318 336[.896 3362.457 3362.988 3363.528 3364.047 3364.5;8 3365.087 3365.587 3366.072 3366.553 3367.026 3367.498 3367.947 3368.401 3368.829 3369.251 3369.670 3370.080 3370.477 3370.881 3371.261 3371.631 3371.990 5372.338 3372.683 3373.008 5373.342 3373.662 3373.984 3374.281 3374.576 3374.846 3375.383 3375.636 3375.893 3376.353

3348.145 3348.891 3349.627 3350.355 3351.073 3351.782 3352.482 3353.174 3353.855 3354.528 3355.192 3355.847 3356.492 3357.129 3357.756 3358.375 3358.984 3359.584 3360.175 3360.757 3361.329 3361.893 3362.448 3362.993 3363.529 3364.056 3364.575 3365.384 3365.583 3366.074 3366.556 3367.028 3367.492 3367.946 3368.391 3368.827 3569.254 3369.672 3370.081 3370.481 3370.871 3371.253 3371.625 3371.989 3372.543 3372.688 3373.024 3373.351 3373.669 3373.978 3374.278 3374.568 3374.850 3375.122 3375.386 3375.640 3375.886 3376.122 3376.350 3376.568 3376.777

-0.6 -0.2 0.2 0.7 1.9 -1.3 -0.8 0.3 0.2 -0.5 -0.2 1.0 0.9 -0.6 -0.8 0.2 0.5 0.6 -0.9 -0.6 -i.I 0.3 0°9 -0.5 -0oi -I.0 0.5 0.3 0.3 -0.2 -0.3 -0.2 0.7 0.I 1.3 0. I -0.3 -0.3 -0.1 -0.4 1.0 0.8 0.6 0.i -0.5 -0.5 -1.6 -0.9 -0.7 0.6 0.4 0.8 -0.4 -0.3 -0.5 0.7 0.3

3540.628 3342.848 3345.056 3344.299 3343.479 3342.666 3341.855 3341.033 334u.189 3339.344 3338.498 3337.629 3336.749 3335.867 3334.989 3334.095 5333.[78 3332.265 3331.333 3330.398 3329.461 3328.496 3327.542 3326.574 3325.587 3924.601 3323.604 3322.590 33Z1.574 3320.570 3319.520 3318.483 3317.428 3316.364 3315.302 3314.214 3315.132 3312.038 3310.927 3309.824 3308.693 3307.568 3306.4?7 33u5.276 3304.127 3302.941 3301.790 3299.401 3298.202 3296.985 3295.773 3294.535 3293.318 3292.058 3290.817 3289.549 3288.287 3286.998 3285.712 3284.412 3283.094 3281.803 3280.475 3279.142 3277.805 3276.456

-~.2 0.0 -0.7 -0.0 -i.i 3.8 -0.7 0.6 -0.0 G.9 -O.l 0.I -0.3 -1.5 0.8 0.3 0.1 0.3 0.2

INFIIAI/,ED B A N D S OF

TABLE X

O B S E R V E DAND CALCULAIEO

N2180

4;~

-I WAVE NUMBERS (VAC.CM. ) 0

OF IHE ROTATIONAL

iB

STRUCTURE OF THE 02

0 15 18 1 - 0 0 0 SAND OF N 0. 2

............................................................ ............................................................ J R(J)OBS R|J)CALC O-C P(J)OBS P(J)CALC G-C XlO0 XlO0 ............................................................ 0 I 2 3 4 5 6 T 8 9 i0 ii 12 13 14 I5 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 43 49 50 51 52 53 54 55 56 57 58 59

3247.532 3248.289 3249.035 3249.768 3250.518 3251.247 3251.965 3252.693 3253.420 3254.128 3254.833 3255.549 3256.246 3256.938 3257.631 3258.327 3259.006 3259.678 3260.355 3261.033 3261.689 3262.341 3262.998 3263.658 3264.297 3264.929 3265.566 3266.207 3266.826 3267.440 3268.053 3268.671 5269.275 3269.868 3270.458 3271.054 3271.641 3272.218 5272.785 3273.352 3273.923 3274.478 5275.023 3275.563 3276.103 3276.647 3277.172 5277.698 3278.208 3278.717 3279.228 5279.732 3280.704 3281.191 5281.660 3282.123 3282.590

3246.780 3247.535 3248.286 3249.032 3249.773 3250.510 3251.243 3251.97I 3252.695 3253.414 3254.129 3254.839 3255.545 3256.246 3256.942 3257.634 3258.322 3259.004 3259.682 3260.355 3261.024 3261.688 3262.347 3263.001 3263.651 3264.295 3264.935 3265.569 3266.199 3266.824 3267.444 3268.058 3268.668 3269.272 3269.871 3270.465 5271.054 3271.637 3272.215 3272.788 3273.355 3273.917 3274.474 3275.024 3275.569 3276.109 3276.643 3277.171 3277.693 3278.210 3278;121 3279.226 3279.725 3280.218 3280.705 3281.186 3281.661 3282.130 3282.992 3283.049

-0.4 0.3 0.4 -0.6 0.7 0.4 -0.7 -0.2 0.6 -0.i -0.6 0.4 0.0 -0.4 -0.3 0.6 0.2 -0.5 -0.0 0.9 O.I -0.6 -0.3 0.7 0.2 -0.5 -0.3 0.8 0.2 -0.4 -0.5 0.3 0.3 -0.4 -0.7 -0.0 0.4 0.3 -0.4 -0.3 0.6 0.4 -0.i -0.7 -0.6 0.4 0.1 0.4 -0.2 -0.4 0.2 0.7 -0.i 0.5 -0.I -0.6 -0.3

3245.267 3244.481 3243.718 3242.946 3242.153 3241.370 3240.595 3239.784 3238.982 3238.198 3237.373 3236.564 3235.754 3234.931 3234.094 3233.277 3232.441 3231.598 3230.763 3229.910 3229.054 3228.202 3227.338 3226.471 3225.604 3224.720 3223.847 3222.964 3222.067 3221.177 3220.279 3219.372 3218.465 3217.547 3216.628 3215.704 3214.777 3213.844 3212.902 3211.957 3211.013 3210.053 3209.096 3208.130 3207.160 32~6.189 3205.201 3204.221 3203.227 3201.227 320u.221 5199.208

3245.258 3244.490 3243.717 3242.940 3242.159 3241.374 3240.584 3239.789 3238.990 3238.187 3237.380 3236.567 3235.751 3234.930 3234.I04 3233.275 3232.440 3231.601 3230.758 3229.910 3229.057 3228.200 3227.338 3226.472 3225.601 3224.725 3223.845 3222.960 3222.070 3221.175 3220.276 3219.371 3218.462 3217.548 3216.629 3215.705 3214.776 3213.842 3212.903 3211.959 3211.010 5210.056 3209.096 3208.131 3207.161 3206.1B6 3205.205 3204.219 3203.228 3202.231 3201.228 5200.220 3199.207 3198.187 3197.163 3196.152

1.0 -0.9 O.I G.6 -0.6 -0.4 l.I -0.5 -0.8 I.I -0.6 -0.4 0.3 0.I -I.I 0.3 0.1 -~.4 J.5 -0.0 -6.4 G.2 -o.i -u.l 0.3 -¢.5 0.2 0.4 -0.3 0.i L.4 C.O 6.3 -0.I --0.i -0.i 0.0 0.2 -0.2 -0.3 J.3 -0.3 -0.0 -c.2 -(,.i ;.3 -~.4 t.2 -%.0 -iJ.l J.i 0.I

.46

GRIGGS, ET AL.

TABLE

OF

?HE

XI

OBSERVEO

RU?AT[ONAL

AND

S~RUCTU~E

CALCULAIED

OF

[HE

II

wAVE

NUMBERS

I

i 1-01

-I (VAC.CM. 15

0 BAND

OF

18 N

0. 2

............................................................ ............................................................ d R(J)OBS R(J}CALC O-C P{J)08S P(J}CALC XIO0 ............................................................ 0 I 2 3 4 5 6 7 8 9 10 Ii 12 13 14 15 16 17 I8 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49

3342.856 3343.594

3345.757 3346.457 3347.157 3347.837 3348.508 3349.181 3349.845 3350.493 3351.770 3352.391 3353.006 3353.620 5354.201 3354.795 3355.384

3357.607 3358.146 3358.670 3359.198

336[.639 3362.113

3364.325

3342.855 3343.594 3344.323 3345.044 3345.756 3346.459 3347.153 3347.838 3348.515 3349.183 3349.842 3350.492 3351.134 3351.766 3352.390 3353.005 3353.612 3354.209 3354.798 3355.378 3355.949 3356.511 3357.064 3357.609 3358.145 3358.672 3359.190 3359.700 3360.201 3360.692 3361.176 5561.650 3362.116 3362.573 3363.021 3365.460 3363.891 3364.312 3364.726

O.I O.C

0.I -0.i 0.4 -0.2 -0.7 -0.2 0.3 0.1 0.3 0.0 0.0 0.9 -0.8 -0.3 0.6

-O.B 0.i -0.2 0.5

-i.1 -0.3

1.2

3339.812 3339.033 3338.249 3337.444 3336.633

3334.147 3333.312 3332.463 3331.589 333D.725 3329.857 3328.965 3328.065 3327.164 3326.249 332b.326 3324.399 3325.459 3322.510

3319.609 3318.635 3317.637 3316.633 3315.638 3314.611 3313.572 3512.557 3311.515 3310.468 3309.406 3308.323 3307.253 3306.166 3305.069 3303.975

3297.1~2 3296.016 3294.827

3339.815 3339.033 3338.242 3337~442 3336.634 3335.816 3334.990 3334.156 3333.312 3332.460 3311.599 3330.729 3329.851 3328.964 3328.068 3327.163 3326.250 3325.328 3324.397 3323.458 3322.509 3321.553 3320.587 3319.613 3318.630 3317.639 3316.639 3315.650 3314.613 3313.587 3312.582 3311.509 3310.457 3309.397 3308.328 3307.250 3306.164 5305.070 3303.966 3302.855 3301.735 3300.6G6 3299.469 3298.323 3297.169 3296.006 3294.835 32<)3.655

F}-C XlO0

-~.3 ~.0 3.7 G.2 -J.O

-J=8 O.O 6.3 -1.O -0.4 u.6 6.1 -b.3 O.1 -~-I -C.2 0.2 0.1 0.1

-¼J.4 4.5 -!.2 -L.6 u.2 -0.2 -~.5 O.B J.6 i.I (,.9 -~,.5 Li.3 C.I -~.I G.8

-1.6 1.0 -3.8

I N F R A R E D BANDS OF

TABLE

OF T H E

XII

OBSERVED

ROTATIONAL

AND

CALCULATED

STRUCTURE

OF

THE 0 3

16

N2180

WAVE

NUMBERS

I

I I-Ol

47

-I (VAC.CM. ) 15

o BAND

OF

18 N

O. 2

............................................................ ............................................................ J R(J)[]BS R{J}CALC O-C P(J}OBS P(J)CALC O-C XIO0 XIO0 ............................................................ 0 1 2 3 4 5 6 7 8 9 I0 iI 12 13 14 [5 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

3226.684

3228.926 3229.658 3230.398 32131.120 3231.839

3234.682 3235.389 3236.079 3236.760

3239.475 3240.142 3241.460 3242.103 3243.401 3244.032 3245.294 3245.924

3248.347 3248.941 3249.530 3250.701 3251.271 3251.837

3226.688 3227.438 3228.184 3228.925 3229.662 3230.393 3231.121 3231.843 3232.561 3233.274 3233.982 3234.685 3235.384 3236.078 3236.768 3237.452 3238.132 3238.807 3239.477 3240.142 3240.803 3241.458 3242.109 3242.755 3243.396 3244.032 3244.063 3245.289 3245.910 3246.527 3247.138 3247.744 3248.345 3248.941 3249.532 3250.118 3250.699 3251.274 3251.845

-0.4 3223.646 3222.872 0.1 -0.4 0.5 -0.i -0.4

-0.3 0.4 0.i -0.8

-0.2 0.0

3221.300 3220.516 3219.724 3218.926 3218.129 3217.316 3216.512

3213.221 3212.378 3211.546 3210.702 3209.846 3208.141

0.2 -0.6 0.5 -O.O 0.5 1.4

0.2 -0.I -0.2 0.3 -0.3 -0.7

3206.414 3205.536 3204.661 3203.783 3202.891 3202.010 3201.107 3200.203 3199.303 3198.385 3197.478 3196.549 3195.632 3194.707 3192.830 3191.884 3190.929 3189.983

3223.639 3222.865 3222.087 3221.304 3220.516 3219.724 3218.927 3218.125 3217.319 3216.508 3215.692 3214.872 3214.047 3213.217 3212.383 3211.544 3210.700 3209.852 3208.999 3208.141 3207.278 3206.411 3205.539 3204.662 3203.781 3202.896 3202.005 5201.108 3200.207 3199.301 3198.391 3197.476 3196.556 3195.631 3194.701 3193.767 3192.827 3191.882 3190.933 3189.978

5.7 0.7 -0.4 0.0 G.G -0.I 0.4 -D.2 0.5

0.4 -0.5 0.3 0.2 -0.6 -0.0 U.3 -U.3 -¢.i 0.2 -0.3 0.6 -t~.l -0.4 0.2 -0.6 0.2 -0.7 0.i U.6 0.3 0.2 -0.4 0.4

48

GRIGGS, ET AL.

TABLE XIII

OBSERVED

OF THE R O T A T I O N A L

AND

CALCULATED

STRUCTURE

OF THE Ol

WAVE

NUMSERS

-[ (VAC.CM. )

Ic n I-O r, 0 HAND OF

15

18 N

O. 2

............................................................ ............................................................ J R[J]OBS R{J)CALC O-C PlJ)OBS P|J}CALC (;-C XIO0 XIOO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

0 1 2 3 4 5 6 7 8 9 I0 Ii 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 2g 30 31 32 33 34 35 36 37 3S 39 40 41 42 43 44 45 46 47 48 4Q 50 51 52 53 54 55 56 57

2702.390 2703.129 2703.867 2704.619 2705.352 2706.077 2706.799 2707.523 2708.230 2708.940 2709.648 2710.334 2711.026 2711.709 2712.397 2713.061 2713.731 2714.395 2715.042 2715.699 2716.340 2716.982 2717.619 2718.236 27~8,857 27~9.474 2720.081 2720.692 2721.284 2721.874 2722.462 2723.047 2723.617 2724.193 2724.756 2725.309 2725.864 2726.407 2726.943 2727.482 2728.019 2728.527 2729.049 2729.563 2730.069 2730.563 2731.062 2731.542 2732.025 2732.501 2732.974 2733.430 2733.905 2734.347 2734.783 2755.219 2735.673

2702.382 2703.135 2703.881 2704.622 2705.357 2706.086 2706.810 2707.527 2708.240 2708.946 2709.641 2710.342 2711.031 2711.715 2712.393 2713.065 2713.732 2714.393 2715.048 2715.697 2716.341 2716.979 2717.611 2718.237 2718.858 2719.473 2720.082 2720.686 2721.283 2721.875 2722.462 2723.042 2723.617 2724.186 2724.749 2725.306 2725.858 2726.404 2726.944 2727.478 2728.007 2728.529 2729.046 2729.557 2730.063 2730.562 2731.056 2731.544 2732.026 2732.503 2732.973 2733.438 2733.897 2734.350 2734.797 2735.239 2735.674 2736.104

0.7 -0.6 -1.4 -0.2 -0.5 -0.9 -[.I -0.5 -l.O -0.7 0.1 -0.8 -9.5 -0.6 0.4 -0.4 -0.i 0.2 -0.6 0.2 -0.i 0.3 0.8 -0.2 -0.2 0.i -0.2 0.7 O.C -0.I 0.I 0.5 0.0 0.7 0.7 0.3 O.& 0.3 -0.I 0.4 1.2 -0.2 0.3 0.5 0.6 OiO 0.5 -0.2 -0.2 -0.I 0.| -0.8 0.8 -0.3 -i.5 -2.0 -0.I

2699.336 2698.547 2697.733 2696.957 2696.149 2695.374 2694.550 2693.743 2692.916 2692°093 2691.259 2690.425 2689.584 2688.721 2687.887 2687.023 2686.168 2685.287 2684.416 2683.529 2682.635 2681.746 2680.846 2679.946 26t9.024 2678.106 2677.195 2676.260 2625.323 2674.387 2673.450 2672.488 2671.538 2670.582 2669.620 2668.642 2667.668 2666.682 2665.710 2664.702 2603.715 2602.711 2661.718 2660.653 2659.637

2656.551

2700.092 26975318 2608.537 2697.751 2696.959 2696.162 2695.359 2694.550 2693.736 2692.916 2692.090 2691.259 2690.422 2689.579 2688.731 2687.877 2687.017 2686.152 2685.281 2684.405 2683.523 2682.635 2681.742 2680.843 2679.939 2679.029 2678.113 2677.192 2676.265 2675.332 2674.394 2673.450 2672.501 2671.546 2670.586 2669.629 2668.648 2667.671 2666.688 2665.700 2664.706 2663.706 2662.701 2661.691 2660.674 2659.653 2658.625 2657.593 2656.554 2655.5[3

1.6 0.9 -[.8 -0,2 -1.3 1.5 -0.0 0.7 0.0 0.3 0.0 0.3 0.5 -i.O 1.0 0.6 1.5 O.b [.i 0.6 -0.o 0.4 0.3 0.7 -0.4 -U.7 O.l -0.5 -0.9 -0.7 -¢.i -[.3 -O.g -0.3 O.C -0.7 -0.3 -0.6 l.G -0.4 0.8 O.g 2.7 -1.7 -1.6

-C.~

INFIIAtlI~;D BANDS 0t~' l~N~aO

TABLE XIV

49

OBSERVED AND CALCULATED WAVE NUMBERS (VAC. CM -I)

OF THE ROTATIONAL STRUCTURE OF THE 011dl - 0000 BAND OF 15N2180

J 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 A8 49 50

Q(J)obs

2700.106 2699,993 2699.869 2699.741 2699.614 2699.479 2699.334 2699.193 2699o041 2698.888 2698.739 2698.568 2698.417 2698.249 2698.072 2697°890 2697.522 2697.327 2697.136 2696°743 2696.530 2696.326

Q(J)calc 2700.332 2700°223 2700.109 2699.991 2699.869 2699.742 2699.611 2699°476 2699°337 2699.193 2699.045 2698.893 2698.736 2698.576 2698.411 2698.242 2698.069 2697.891 2697°709 2697.524 2697.334 2697.139 2696o941 2696.739 2696.532 2696.322 2696.107

(o-c)xl00

-0.3 0.2 0.0 -0oi 0,3 0.3 -0.3 0°0 -0.4 -0.5 0.3 -0.8 0.6 0.7 0.3 -0oi -0.2 -0.7 -0.3 0.4 -0.2 0.4

GRIGGS, ET AL.

50

T A B L E XV

OF

THE

OBSERVED

ROTATIONAL

AND CALCULATED

STRUCTURE

OF

THE

WAVE

NUMBERS

0 0 20 0 - 0 0 0 BAND

-I (VAC.CM. ) 15 OF

18 N

O. 2

............................................................ ............................................................ J R(J)[IBS R(J)CALC O-C P(J)OBS P[J)CALC O-C x100 XIOO ..............................................................

2 3 4 5 6 7 8 9 I0 ii 12 13 14 I5 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 85 56 57 58 59 60 61 62

2447.943 2448.688 2449.436 2450.178 2450.913 2~51.650 2453.100 2453.806 2454.504 2455.203 2455.904 2456.586 2~57.273 2457.958 2458.622 2459.296 2459.957 2460.609 2461.264 2461.906 2462.540 2463.184 2463.811 2464.424 2465.043 2466.274 2466.852 2467.452 2468.042 2468.621 2469.198 2469.782 2470.340 2470.896 2471.449 2472.001 2472.556 2473.082 2473.616 2474.129 2474.663 2475.186 2475.698 2476.200 2476.708 2477.215 2477.691 2478.175 2479.129 2479.595 2480.511 2480.974 2481.400 2481.867

2447.94G 2443.692 2449.439 2450.180 2450.915 2451.645 2452.369 2453.087 2453.800 2454.506 2455.208 2455.903 2456.593 2457.277 2457.955 2458.628 2459.295 2459.956 2460.612 2461.262 2461.906 2462.845 2463.178 2463.805 2464.427 2465.043 2465.654 2466.259 2466.858 2467.452 2468.040 2468.623 2469.200 2469.771 2470.337 2470.898 2471.452 2472.002 2472.546 2473.084 2473.617 2474.145 2474.667 2475.184 2475.695 2476.201 2476.701 2477.197 2477.687 2478.171 2478.65i 2479.125 2479.593 2480.057 2480.515 2480.969 2481.417 2481.859 2482.297 2482.730

0.3 -0.~ -0.2 -0.2 -0.2 0.5 1.3 0.6 -0.2 -0.4 0.I -0.7 -0.4 0.3 -0.6 0.i 0.I -0.3 0.2 -0.0 -0.5 0.6 0.6 -0.4 -0.i 1.6 -0.6 -0.0 0.2 -0.2 -0.2 i.I 0.3 -0.2 -0.3 -0.I I.I -0.2 -0.2 -1.6 -0.4 0.2 0.3 -0. I 0.7 1.8 0.5 0.4 0.4 0.i -0.5 0.5 -1.7 0.8

2446.406 2445.638 2444.871 2444.098 2443.B04 2442.518 2441.718 244J.911 2440.115 2439.288 2438.472 2437.641 2436.798 2435.975 2435.125 2434.286 2433.425 2432.574 2431.705 2430.838 2429.956 2429.076 2428.191 2427.297 2426.404 2425.492 2424.586 2423.671 2422.756 2421.826 2420.899 2419.959 2419.022 2418.066 2417.120 2416.161 2415.198 2414.229 2413.254 2412.278 2411,294 2410.309 2409.309 2408,313 2407.306 2406,301 2405,283 2404,265 2403,251 2402,214 2401,170 2400.131 2399.085 2398,049 2397,000 2395.944 2394.860 2392,738

2389,487

2446.418 2445.649 2444.873 2444.093 2443.306 2442.514 2441.716 2440.913 2440.104 2439.289 2438.469 2437.643 2436.811 2435.974 2435.13i 2434.283 2433.429 2432.569 2431.704 2430.834 2429.958 2429.076 2428.189 2427.296 2426.398 2425.494 2424.585 2423.671 2422,751 2421.826 2420.895 2419,959 2419.017 2418,071 2417,118 2416.161 2415.198 2414.231 2413.257 2412.279 2411,295 2410,307 2409,313 2408,314 2407.310 2406.300 2405,286 2404.267 2403.242 2402.213 2401.179 2400.139 2399.095 2398.046 2396.992 2395.933 2394.870 23')3.801 2392.728 2391.650 2390.568 2389.481

-1.2 -I.I -0.2 0.5 -0.2 0.4 0.I -0.2 1.1 -0.I 0.3 -0.2 -£.3 G.l -D.6 0.3 -0.4 0.5 0.I 0.4 -0.2 -O.O 0.2 0.0 0.6 -0.2 G.O O.l 0.5 0.0 0.4 0.0 0.5 -0.4 0.2 0.0 -0.0 -0.2 -0.3 -O.I -0.I 0.2 -0.4 -0.I -0.4 U.O --0.3 -0.2 6.8 0.i -0.9 -0.9 -I.0 U.3 0.8 i.i -i.0 1.0

~.6

I N F R A R E D B A N D S OF

TABLE

OF

THE

XVI

OBSERVED

ROTATIONAL

AND CALCULATED

STRUCTURE

OF

THE

21

15

N~18O

WAVE

NUMBERS

I

I 0-01

,51

-I IVAC.~CM. ) 15

0

BAND

UF

18 N

O. 2

............................................................ ............................................................

J R(J}08S R(J)CALC O-C P(J)08S XIO0 ............................................................

P(J)CALC

[J-C xlo~

O I 2463.343 2463.348 -O.b 2 2464.106 2464.09? 0.8 2460.299 3 2464.840 2464.841 -0.I 2459.518 2459.524 -0.5 4 2465.580 2458.748 2458.745 0.5 5 2466.313 2457.958 6 2467.036 2467,041 -0.5 2457o178 2457.167 [.2 ? 2467.770 2467.764 0.5 2456.374 2456.370 0.4 8 Z468.483 2468.482 0.i 2455.585 2455.569 1.6 9 2469.194 2454.?54 2454.762 -0.8 -0.2 I0 2469.901 2469.901 -0.I 2455.948 2453.950 II 2470.608 2470.603 0.4 2453.133 12 2471.299 2471.300 -0.1 2452.311 13 2472.001 2471.991 1.0 2451.483 2451.484 -0.0 14 2472.662 2472.67? -1.5 2450.644 2450.651 -0.8 15 2473.360 2473.358 0.2 2449.811 2449.814 -0.2 16 2474.034 2448.965 2448.971 -U.6 17 2474.?04 2448.125 2448.123 9.2 18 24?5.362 2475.369 -0.7 2447.260 2447.270 -l.O 19 2476.031 2476.029 0.2 244b.406 2446.412 -0.5 20 2476.680 2476.683 -0.4 2445.548 21 2477.310 2477.333 -2.3 2444.682 2444.680 ~.2 22 2477.977 2443.814 2443.806 G.? 23 2478.600 2478.615 -1.5 2442.930 2442.927 0.3 24 2479.249 2442.052 2442.044 0.9 25 2479.892 2479.87? 1.5 2441.159 2441.155 t.4 26 2480.499 2480.500 -0.1 2440.261 -0.5 24~9.562 27 2481.114 2481.118 28 2481.719 2481.231 -1.2 2438.458 29 2482.356 2482.338 1.8 2437.549 30 2482.928 2482.940 -1.2 2436.635 31 2483.525 2483.537 -1.2 2455.723 2435.716 0.8 32 2484.158 2484.129 2.g 2434.789 2434.792 -0.5 35 2484.709 2484.715 -0.6 2453.864 2433.863 0.2 2432.92? 2432.929 -0.2 34 2485.296 2485.2g? -0.0 35 2485.875 2485.873 0.2 2451.995 2431.990 i~.6 56 2486.462 2486.444 1.8 2431.04b 37 2486.995 2487.009 -1.4 2430.097 38 2487.549 2487.570 -2.1 2429.143 39 2488.116 2488.125 -i.~ 2428.179 2428.184 -0.6 40 2488.674 2488.676 -0.2 ............................................................

52

GRIGGS, E T A1,.

T A 5 L E XVII

OF

THE

OBSERVEO

RQTATIONAL

AND

CALCULATED

STRUCTURE

OF

THE

20

WAVE

NUMBERS

0

0 0-00

-1 (VAC.CM. ) 15

O BAND

OF

16 N

0. 2

............................................................ ............................................................

J

R(J)OBS

R(J)CALC

O-C

P(J)OBS

PIJ}CALC

O-C XlOO

XlO0 ............................................................

0 I 2

2524.830 2525.649

3

2526.436

4 5 6 7 8 9 i0 II 12 13 14 15 16 17 18 19 20 21 22 23

2527.202 2527.973 2528.733 2529.483 2550.239 2530.986 2531.710 2532.443 2533.172 2533.876 2534.587 2535.289 2535.985 2536.672 2537.353 2538.028 2553.702 2539.356 2540.010

24

2541.307 2541.931 2542.561 2543.191 2543.792 2544.383 2545.000 2545.582 2546.194 2546.762 2547.312 2547.884 2548.455 2549.004 2549.544

25 26 27 28 29 30 31 32 33 34 35 36 37

38 39 40 4I 42 43 44 45 46 47

2540.656

2524.056 2524.853 2525.642 2526.425 2527.201 2527.970 2528.733 2529.488 2530.237 2530.980 2531.715 2532.444 2553.166 2533.881 2534.589 2535.291 2535.985 2536.673 2537.355 2538.029 2538.697 2539.357 2540.011 2540.659 2541.299 2541.933 2542.559 2545.179 2543.793 2544.399 2544.998 2545.591 2546.177 2546.756 2547.328 2547.8g3 2548.452 2549.303 2549.548

2550.086

2550.086

2550.623 2551.132 2551.664 2552.158 2552.681 2553.169 2553.681

2550.617 2551.141 2551.659 2552.169 2552.673 2553.169 2555.659 2554.142

-2.3 0.7 I.i 0.I 0.3 0.1 -0.5 0.2 0.6 -0.5 -0. I 0.6 -0.5 -0.2 -0.2 -0.I -0.2 -0.i -0.i 0.5 -0.I -0.1 -0.2 0.8 -0.2 0.2 i.i -0.i -i.6 0.2 -0.9 1.7 0.6 -1.6 -1.0 0.3 0.I -0.4 0.o 0.6 -0.9 0.5 -1.2 0.8 -0.i 2.2

2522.431 2521.624

2522.444 2521.627

252G.806

2520.804

-i.3 -~.3 0.2

2519.969 25[9.147 2518.293 2517.453

2519.974 2519.137 2518.294 2517.444

-0.5 i.O --0.1 0.9

2516.593

2516.587

2515.715 2514.855 2513.980 2513.099 2512.210 2511.295 2510.410 2509.487 2508.584 2507.647 2506.706

2515.723 2514.853 2513.976 2515.093 2512.202 2511.305 2510.401 2509.491 2508.5Z4 2507.650 2506.719 2505.782 2504.838 2505.887 2502.930 2501.966 2500.996 2500.018 2499.034 2498.044 2497.047 2496.043 2495.052 2494.015

250~.8Z2 2503.885 2502.913 25UI.966

24!)9.025 2498.035 2497.072 2495.042

0.6

-0.9 0.I 0.4 0.6 0.8 -i.O 0.9 -G.4 i.i -0.3 --1.3 -1.7 -6.5 -1.8 0.0

-U.9 -0.9 2.6 1.0

INFRARED BANDS OF T A B L E XVIII

OF T H E

OBSERVED

ROTATIONAL

ANO

CALCULATED

STRUCTURE

OF

~HE

O0

15N~80

WAVE

NUMBERS

0

0 1-00

53 -I (VhC.CM. I 15

0 BAND

OF

18 N

O. 2

............................................................ ............................................................ J RIJ)OBS RIJ)CALC 11-C P{J)OBS P[J)CALC i3-C XIOD XIOO ............................................................ 0 1 2 3 4 5 6 7 8 9 IO Ii 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 DO 51 52 53 54 55 b6 57 58 59 60 61 62 63 64 65

2148.360 2149.093 2149.832 2150.584 2151.321 2152.044 2152.771 2153.472 2154.188 2154.89b 2155.591 2156.277 2156.969 2157.649 2158.317 2158.989 2159.638 2160.291 2160.955 2161.594 2162.216 2162.853 2163.484 2164.080 2164.700 2165.325 2165.915 2166.801 2167.093 2167.673 2168.242 2168.816 2169.378 2169.937 2170.474 2171.018 2171.566 2172.116 2172.621 2173.121 2173.661 2174.156 2174.669 2175.147 2175.638 2176.129 2176.613 2177.078 2177.536 2177.968 2178.443 2178.889 2179.324 2179.749 2180.191 2180.608

2182.614 2183.003 2183.365

2148.346 2149.097 2149.843 2150.582 2151.316 2152.043 2152.765 2153.480 2154.189 2154.892 2155.589 2156.280 2156.965 2157.o44 2158.316 2158.983 2159.643 2160.297 2160.946 2161.588 2162.224 2162.854 2163,477 2164.095 2164.707 2165.312 2165.911 2166.504 2167,091 2167.672 2168.246 2168.815 2169.377 2169.933 2170.483 2171.027 2171.565 2172.096 2172.622 2173.141 2173.654 2174.160 2174.661 2175.155 2175.644 2176.125 2176.601 2177.071 2177.534 2177.991 2178.442 2178.887 2179.525 2179.757 2180.183 2180.603 2181.017 2181.424 2181.825 2182.220 2182.608 2182.991 2103.367 2183.136 2184.100 2184.457

1.5 -0.5 -i.I 0.2 O.D 0.I 0.7 -0.8 -0.3 0.4 0.2 -0.3 0.4 0.5 !3.0 0.6 -0.5 -0.7 0.9 0.6 -0.8 -0. I 0.7 -1.5 --0.7 1.3 0.4 -0.3 0.2 0.i -0.5 0. i 0.i 0.3 -0.9 -0.9 0.I 2.0 -3.0 -1.9 0.7 -0.4 0.8 -0.9 -0.5 0.3 1.2 0.8 0.2 -2.4 0.i 0.3 -0.i -0.9 O.l 0.4

0.6 1.3 -0. I

2146.830 2146.057 2145.273 2144.502 2143.707 2142.909 2142.114 2141.307 2140.500 2139.670 2138.860 2138.026 2137.192 2136.350 2135.490 2134.649 2133.783 2132.913 2132.056 2131.167 2136.293 2129.397 2128.503 2127.890 2126.686 2125.776 2124.852 2123.941 2122.998 2122.062 2121.117 2120.167 2119.207 2118.251 2117.282 2116.303 2115.324 2114.358 2113.357 2112.358 2111.354 2110.346 2109.322 2108.315 2107.284 2106.244 21Eb.211 2104.146 2103.133 21~2,086 2100.999 2099.926 2098.862 2097.783 2096.701 2095.605 2094.504 ~093.395 2092.300 2091.180 209d.061 2J8~.926 2087.810 2086.680

2146.824 2146.055 2145.279 2144,497 2143.709 2142.915 2142.I15 2141.309 2140.497 2139.679 2138.855 2138.025 2137.189 2136.347 2135.499 2134.645 2133.785 2132.919 2132.047 2131.169 2130.285 2129.395 2128.499 2127.597 2126.689 2125.775 2124.856 2125.930 2122.998 2122.061 2121.117 2120.167 2119.212 2118.251 2117.283 2116.310 2115,331 2114.346 2113.355 2112.358 2111.355 2110.346 2109.331 2108.311 2107.284 2106.252 2105.215 2104.169 2103.119 2102.063 2101.OOl 2099.934 2098.860 2097.781 2096.695 2095.604 2994.507 2093.404 2092.296 2391.181 2090.061 2088.935 2087.802 2086.605 2085.521

G.5 3.2 -~.6 3.5 -0.2 -~.6 -~.i -0.2 0.3 -6.9 0.4 ~.0 5.3 0.3 -0.9 U.4 -C.2 -0.6 J.9 -0.2 0.8 3.2 6.4 -G.7 -J.4 O.0 -U.3 I.I -0.0 ~.I u.O -0.0 -4.5 ~.i -U.I -0.7 -~.7 1.2 u.2 0.0 -D.l 0.0 -0.9 ".4 -0.0 -0.8 -~.2 -Z.3 1.4 2.3 -J.3 -0.8 ~.2 4.2 5.5 0.I -~.3 --I.i J.4 -~,.I 6.1 -~.9 b.8 1.5

54

GRIGGS, ET AL.

T A B L E XIX

OF

THE

OBSERVED

ROTATIONAL

AND

CALCULATED

STRUCTURE

UF

[HE

Ol

WAVE

NUMBERS

I

I 1-01

-i (VAC.CM. ] 15

0 BAND

OF

18 N

O. 2

........................................................... ............................................................ J R|J}OBS R[J}CALC U-C P[J}OBS P[JICALC XlO0 ............................................................ 0 1 2135.906 2135.927 -Z,l 2 2136.685 2136.673 1.2 2132.880 3 2137.403 2137.414 -1.2 2132.104 k 2138.149 2131.331 2131.321 5 2138.877 2130.538 2130.533 6 2139,600 2129.739 2129.738 7 2140.315 2140.317 -0.2 2128.941 2128.938 8 2141.028 2141.027 0.0 2128.131 2128.131 9 2141.726 2141.732 -0.7 2127.310 2127.319 i0 2142.437 2142.431 0.6 2126.510 2126.50I ]] 2143.116 2143.124 -0.7 2125.676 2125.676 12 2143.786 2143.810 -2.4 2124.846 13 2144.491 2124.010 14 2145.177 2145.165 1.2 2123.165 2123.168 15 2145.833 2145.834 -0.1 2122.321 2122.320 16 2146.506 2146,497 0.9 2121.466 2121.466 17 2147.156 2147,153 0.3 2120.607 2120.606 18 2147.799 2147.804 -0.5 2119.741 2119.740 19 2148.448 2148.448 -0.i 2118.869 2118.868 20 2149.093 2149.087 0.6 2117.993 2117.990 21 2149.720 2149.719 0.i 2117.108 2117.106 22 2150.346 2150.346 0.i 2116.227 2116,216 23 2150.969 2150.966 0.5 2115.324 2115,321 24 2151.575 2151.581 -0.5 2114.400 2114,419 25 2152.194 2152.18g 0.5 2113.501 2113.512 26 2152.791 2112.598 2112.598 27 2153.387 2111.673 2111,679 28 2153.991 2153.978 1.3 2110.754 2110,75~ 29 2154.562 2154.562 0.0 2109.818 2109.822 30 2155.135 2155.140 -0.7 2108.886 2108.885 31 2155.712 2107.940 2107,942 32 2156.278 2107.003 2106,993 33 2156.825 2156.838 -1.3 2106.033 2106.038 34 2157.392 2157,392 0.0 2165.076 2105,078 35 2157.926 2157.940 -1.4 2104.108 2104,111 36 2158.484 2158.482 0.3 2103.138 37 2159.017 2102.160 38 2159.547 2101.182 2101.175 39 2160.072 2160.070 0. I 2100.184 2100,185 40 2[60.586 2160.588 -0.2 2099.]87 2097.189 41 2161.099 2098.177 2098.187 42 21ol.605 2097.178 2097.179 43 2162.104 2096.177 2096.165 44 2162.609 2162.597 1.2 2095.141 2095.145 45 2094.103 2094.120 46 2095.095 2093.088 47 2092.026 2092.051 48 2091.030 2091.007 49 2089.958

f~-C X100

1.0 6.5 0.1 0.3 -0.I -0.9 0.9 -O.G

-Q.Z 0.1 0.0 0.i 0.I 0.1 0.3 0.2 i.O 0.3 -2.0 -1.I -0.0 -u,O 0.0 -u.4 O.l -~.2 1.0 -u.6 -0.2 -0.3

0.7 -0.1 -0.2 -i.0 --0.0 1.2 -0,4 -1.6 0.7 --Z.5 2.3

INFRARED BANDS OF

i$

N 2180

55

TABLE XX MEASUREMENTS (VaCo cm-I) OF THE RESOLVED ~-TYPE DOUBLETS

J 8 9 I0 II 12 13 14 15 16 17 18 19 20 2[ 22 23 24 25 26 27 28 29 3O 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

211ci-011c0 BAND

211dl-olldo BAND

031ci~011c0 BAND

031dl-011d0 BAND

R(J)

R(J)

K(J)

R(J)

P(J)

P(J)

p(J)

3231~806 3233°933 3234°624 3235°320 3236°003 3236°670 4554.928 4555.487 4556.043 4556,584

4556°443 4556°969 4557.480

4560.302 4560.727

4523.083 4522°082 4521.051 4519o994 4518.926 4517.869 4516.781 4515~682 4514.571 4513.461 4512.326 4511.182

4559o161 4559°636

4561.451

3238Q030 3238.688 3239.343 3239°996 4523.207 4522o201 4521.167 4520o133 4519.079 4518o011 4516.962 4515o879 4514o771 4513o683 4512.561 4511o441

3241o292 3241.917 3242°552 3243o190 3243.801 3244,418 3245.028 3245°640

3247.993 3248°569 3249,137 3250.261 3250o814 3251o360 3252.427 3252°958

3231.872 3232.595

3214.009 3213.174 3212.324 3211o482 3210.627 3209.758 3208.906 3208.036 3206.287 3205.398 3204.511 3203.617 3202.711 3201o810 3200°894 3199o980 3199°063 3198.128 3197.211 3196o264 3195.322 3194.$77 3192.467 3191.493 3190.525 3189o550

3234.740 3235°457 3236o156 3236.850 3237.550

3239°607 3240°289 3240°967 3241,628 3242°290 3243.612 3244.262 3245,560 3246.208 3248°083 3248o701 3249.312 3249°923 3251o142 3251.728 3252.314 3252.904 3254°643 3255. 203

3254°509 3255o015

P(J)

3214,903 3213o267 3212.431 3211o611 3210.777 3209.933 3208.245 3207°389 3206o541 3205,674 3204.812 3203°949 3203.072 3202.210 3201.320 3200°426 3199o544 3198o642 3197.745 3196.835 3195o943 3195.037 3194o110 3193.192 3192.276 3191o332 3190o416 3189~468

56

GRIGGS, ET AL.

TABLE XX (Continued) MEASUREMENTS

J 8 9 i0 ii 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51

(vaco cm -I) OF THE P~ESOLVED ~-TYPE DOUBLETS

lllCl-ollC0 BAND

llldl-011d0 BAND

211d0-011d0 BAND

211c0-011c0 BAN~

R(J)

~(J)

R(J)

R(J)

p(J)

P(J)

P(J)

2472.709 2473.408 2474,763 2475°440 2476.105 2476.742 2477.405

3355o417 3355.989

2478.685

3357.024 3357.557 3358°094 3358.610 3359o134

3357.658 3558.198 3358.730 3359°256 3359,762

3360o619 3361~097 3361o568 3362,029

3363°354 3363.799 3364.209

3310.432 3309°376 3308°288 3307.211 3306.115 3305o018 3303.920 3302.782 3301.683

3297.085 3295°930 3294.745

3361.711 3362,197 3362,660 3363.113

3364.441 3364.835

3310.504 3309.435 3308.357 3307,295 3306.216 3305.119 3304.030

2472.616 2473.312 2473.983

2444.725 2443.864 2442°985 2442.112 2441.232 2440°342 2439.443

2435°839 2434°909 2434°000 2433°072 2432o149 2431.201 2430.275 2429.320 2428.374

2475°283 2475.956 2476.617 2477.215 2477.880 2478,516 2479.129 2479.753 2480°368 2480.974 2481o571 2482o217 2482.748 2483°355 2483°969 2484,511 2485.086 2485,652 2486°205 2486.718 2487°272 2487.827 2488°404 2488°944

2490.074 3300.668 3299.538 3298.397 3297.220. 3296.102 3294.909 3292.548

3291.184

2480,031 2480°630 2481.253 2481o867 2482°496 2483.109 2483.696 2484.347 2484°908 2485,506 2486°098 2486.718 2487°272 2487.827 2488.404 2488°944

P(J)

2489°959

2445.516 2444.638 2443.763 2442°875 2441.993 2441o086

2437.454 2436.538 2435.608 2434,669 2433,728 2432~781 2431o842

2427~ 983 2427.048 2426. 045 2425.055 2424.065 2423°072 2422.040

INFI~ARED BANDS OF

N2180

-~ o~

15

BASIC OBSERVATIONAL D A T A

T h e observed positions appearing in Tables I I I - X I X are average values of at least three scans on each line. F o r the " h o t " bands, the average of the wave numbers of the t w o eomponents of the g-type doublets is given; the wave nun> bers of the resolved double¢s are given in T a b l e X X . T h e following s u m m a r y is intended to furnish a guide t h r o u g h the tables: Spectral region (cm-1) 4565-4485 4292-4202 3693-3540 3376-3190

Bands observed 2v, + va 2v, + v2 + va -- v~ 2va v~ -t- 2va -- v2 3vl 2v~ -4- 2v2 v, + va 2v2 -4- ea

vl

+

v2 +

3v2 q - va - -

Tables III IV V VI VII VIII IX X

v8 -- v2 v2

2736-2656

v2 + va (011q-00°0) v2 + va (Q branch, 0Dq-0000)

2488-2390

2vl

2184-2087

2v~ + v,~ -- v2 va v2 + v~ -- v2

XI

XII XIII XIV XV XVI XVIII XIX

The overtone b a n d 2va formed a b a n d head at about 4290.5 em -I The 0221-0110 ( A - H ) and 02°1-0110 ( Z - I I ) transitions at 2688.7 em -1 and 2678.7 em -1, respectively, were observed b u t n o t resolved. I n view of the long optical p a t h s involved, the small residual a m o u n t s of CO2 and H20 in the p a t h produced interference in the vl + 2v2 region (2390 2300 em -1) and the 3,1 and (2vl + 2v2) region (3693-3540 em-~). 15 16 Finally, the 2vl b a n d of N 2 0 appeared as an i m p u r i t y in the sample and the d a t a pertaining to this b a n d are given in Table X V I I and the molecular constants derived f r o m the observations in a footnote to Table I. INTERNUCLEAR DISTANCES I n this section, a description is presented of the procedure employed for determining equilibrium values for the internuelear distances of the nitrous oxide molecule. A s s u m p t i o n is m a d e t h a t the equilibrium values are not changed b y isotopic substitution. Laurie and tiersehbaeh (7) pointed out the need to consider the influence of vibrations on the determination of molecular structures. However, in the ease of N20 the problem is not serious since their calculations indicate a change of less t h a n 10-4 A in the values of the equilibrium internuclear distances

GRIGGS, ET AL.

58

TABLE ~G
ISOTOPIC SPECIES OF NITROUS OXIDE

MICROWAVE

INFRARED

OBSERVED

BOO00

Be-B0000

Be

Be

(em -I)

(em-I)

(cm-I)

(cm-I)

BooOoXlO'IO (sec -I)

CALCULATED

14NI4NI60

1.256164 b

0.4190109

0.002122c

0.421133d

0.421135 e

15NI4NI60

1.213730

0.4048564

0.002030

0.406886

0.406886

15NI5NI60

1,213739

0.4048594

0.002008

0.406867

0.406865

15NI5NI80

1.144804

0.3818652

0.001856

0.383721

0.383719

14NI5NI60

1.256078

0.4189822

(0.002099)

---

0.421081

14NI4NI80

1.185911

0.3955770

(0.001966)

---

0.397543

14NI5NI80

1.185582

0.395467

(0.001942 )

---

0.397409

15NI4NI80

i~144966

3 0.3819192

(0.'001876)

---

0.383795

amasses referred to 12C scale:

Physical constants:

14N - 14.0030744 AMU

e = 2.997927 x 1010cm/sec

15N - 15.0001081 AMU

h = 6.62540 x lO-27erg-se¢ M I = 1.66038 x 10-24gm/AMU

160 - 15~9949149 AMU 180 - 17.9991598 AMU bValue for 14N2160 is from Refo (8).

Others from Ref. ~_~).

cValues for 14 N^ 16 0 15 N 14 N 16 0 and 15 N~ 16 0 are derived from Ref, (i 2 ,13). . ~rom 'this work= ' Values ~or the remaining i~otopic species -- -Value for 15 N 2 18 O zs are calculated values, based upon B0000 and the calculated values of B e. dThis column contains the sum of the previous two columns. ecalculated from the internuclear distances:

r I = 1.12665 A, and

r 2 = 1.18565 A by Eq, (3).

The first step involves the determination of the equilibrium values for the inertiM constant, Be, in the case of the four isotopic species, 14N~60, 15N'4N160, 15N~60, and ~SN~SO, for which good infrared and microwave measurements are available. The B0o0ovalues determined from microwave investigations (8, 9) have been combined with the (B,--Bo0oo) obtained from infrared measurements in the following way: Using standard notation (10), it is easily seen that Be -- B0000 = ~ , / ( ~ l + 2~2 +

~)

= ½[B~00o + B00Ol -- (BlO0~ +

Bo2oi)].

(1)

F~quation (1) neglects the terms involving ~, 's which are smM1 and do not seem to have any influence within the limits of precision achieved in this work. The

INFRARED

B A N D S O F 1aNglO

A 2,315 o~<

S

--o--- 14N 160 2 15N2180 ~ 15N2160

~

C~/

5,9

/

~

and

+ 2.510 i.._¢,1

2.305

'

~

-0.2 r2 - r,

"'"

" 2.5125 ~

0.2

\

\

~_

(X)

[3 - o ~

14N2160

~

15N2180

2.512'~ ~ o~

,~

0.0

~

--n--- 15N2160

I _ 0.05

I 0.06 0.07 r2 r, (~)

and

-F 2,5122 L¢,,,I 2.N21 2.N20

,._

-

2.31255,

,EL,,. ~~"

C

L_-- 2.:31250. . . . . . . . . . . . . . . .

-o--'4N2'60

~

ond

~_¢xl 2.51225

0,056

0.058

0.060

0.062

r~ - r., (X) FIG. 3. P l o t of i n t e r n u c l e a r d i s t a n c e s of t h e n i t r o u s oxide m o l e c u l e

60

GRIGGS, ET AL. TABLE XXII [NTERNUCLEAI~ DISTANCES OF NIT[~OUS OXIDE (~)a Source

Douglas and M¢ller ~, Pliva ~ This work

rl

r2

1.1257 4- 20

1.186a 4- 20

1.1282 4- 5 1.1266.~ 4- 5o

1.1842 4- 5 1.1856.~4- 50

R1

R2

0.060~

2.312o

0.0560 0.0590 4- 10

2.3124 2.312304- 3

Standard deviations are quoted in units of the last significant figure. b See Reference 11. See Reference 12.

observed B's for the 10°1 and 02°1 states are perturbed values by Fermi resonance, but Eq. (1) involves the sum, B1001 d- B0201, which is not altered b y the perturbation. For employing infrared data effectively, Eq. (1) m a y be rearranged as Be

--

Boooo =

1/~[(Boooo -

Blool) +

(Boooo -- Bo2ol) -- ( B o o o o -

Boo@].

(2)

The AB's appearing in each of the brackets ( ) on the right side of the equation are determined accurately from the measurements of the (vt + v3), (2~2 + ~3), and va bands. Equation (2) allows the evaluation of Be b y combining the microwave B0000with infrared AB's. The values of Be obtained in this manner are given in the Be (observed) column of Table X X I . The next step in the determination of interimelear distances involves the use of Be( = h/87r2cIe) in the equation: I = mxm~h~ + mxmz(h

+ r2) '2 + m y m z r 2 2,

(3)

rr~,x ~- m y -4- ~gz

where I gives the m o m e n t of inertia of a linear X Y Z molecule about an axis passing through the eenter of mass and perpendicular to the figure axis, with r~ and r2 representing the X - Y and Y - Z distances, respectively. I n a two-dimensional (rx, r2) space, the locus of points which reproduce an observed B value is a line. When a line from each of the isotopic species is plotted on the same (r~, r2) graph, the point of intersection determines the internuclear distances. A slight transformation of Eq. (3) proved useffll. Setting (r2 - rl) = R1 and (r2 + rl) R2, one can solve Eq. (3) for R2 in terms of R1 as R2 = [ - b 4- (b 2 -- 4ac)~/2]/2a,

(4)

where a = l~(mxmy + 4mxmz + mymz), b = l ~ m y ( r n z -- m x ) R 1 , c = 1/~4my(mx + mz)R12 -- ( m x -4- m y + Uz)(h/87r2cB).

(5)

I N F R A R E D BANDS OF 15~T ~ t~(~~

61

One may choose m a n y particular values of RI and use Eq. (4) to compute cot responding values for R~. The use of the electronic computer is a great help in making these calculations and plotting the points in a R1-R2 graph. Figure 3 shows the plots made for the four isotopic species; the scale is expanded in steps from Fig. 3(a) to Fig. 3(c). The final choice of the values for the R1 and R2 was made on Fig. 3(e), tbe values obtained being R1 = 0.0590 ~ 0.0010 A and R2 o 2.31230 o± 0.00003 A, resulting in the internuclear distmmes r~ = 1.1266~ ± o 0.00050 A and r2 = 1.1856~ ± 0.0005o A. Large values for the standard deviations have been assigned because of the near dependence of the equations. It is interesting to note that the distance between the end atoms, R2 = r~ 4- r~, is determined about 20 times more accurately than the individuM internuclear distances. Values of B~ calculated from these internuclear distances are presented in the last column of Table X X I . The observed B~'s are reproduced to within ±0.000002 cm--1• Curves in Fig. 3 show that use of the data for the heaviest isotope enables the determination of less ~mbiguous values for the internuclear distances. The various values for the internuclear distances determined thus far are compared in Table X X I I . There is agreeinen~ between the present work and that of Douglas and Moiler within the standard deviations quoted. The discrepancy between Pliva's quoted values and those obtained here appears to be mostly due to the difference in the value used for the quantity Bo - B0000for 14N21~O. RECEIVED: June 1, 1967 REFERENCES 1. JAMES :L. GRIGGS, JR., K. NARAHAR1 RAO, L. H. JONES, AND R. M. POTTER, J. 1~1o[. Spectry. 18, 212 (1965). 2. JAMES L. GRIGGS, JR., K. NARAIIARI RAO, L. I-I. JONES, AND R. M. POTTER, J. Mol.

Spectry. 22, 383 (1967). 3. JAMES :L. GRIGGS, JR., Ph.D. dissertation, The Ohio State University, 1967. ~. K. NARAYIARIRAO, C. J. HUMPHREYS, AND D. H. RANK "Wavelength S t a n d a r d s ia t h e Infrared." Academic Press, New York, 1966. 5. D. ]-]. RANK, D. P. EASTMAN, B. S. RAO, AND W. A. WIGGINS, J. Opt. Soc. A m . 52, 1 (1962). 6. :K. NARAttARI RAO AND ~-IARALDH. NIELSEN, Can. J. Phys. 34, 1147 (1956). 7. VICTOR W. LAURIE AND DUDLEY R. T::[ERSCHBACH,J . Chem. Phys. 37, 1687 (1962). 8. C. A. BI;RRUS AND W. GORDY, Phys. Rev. 101,599 (1956). 9. C. H. TOWNES AND A. L. SCHAWLOW, " M i c r o w a v e

10. 11. 12. 13.

Spectroscopy." McGraw-Hill,

New

York, 1955. G. t]ERZBERG, "Infrared and Raman Spectr~ of Polyatomie Molecules." Van Nostrand, Princeton, New Jersey, 1945. A. E. DOUGLAS AND C. K. MOLLER, J. Chem. Phys. 22, 275 (1954). J. PLIVA, J. Mol. Spectry. 12, 360 (1964). J. PLIVA, J. Mol. Speetry. 5, 62-76 (1967).