M OLECUL A R PH Y SICS , 1998, V OL. 93, N O.

1, 137 144

High resolution far infrared spectroscopy of IBr using a synchrotron

source
By B. NELA NDE R 1 , V. SA BLINSKA S 2, M. DULICK 3 , V. B RA UN 4 and P. F.
BE RNA TH 4
1

Thermochemistry, Chem ical Center, University of Lund, P.O. Box 124, S-22100
Lund, Sweden
2
Departm ent of General Physics and Spectroscopy, Vilnius University, Universiteto
Str. 3, Vilnius, 2734 Lithuania
3
National Solar Observatory, National Optical A stronom y Observatories, PO Box
26732, Tucson, A Z 85726, USA
4
Departm ent of Chemistry, University of Waterloo, Waterloo, Ontario, Canada
N2L 3G1
( Received 15 July 1997; accepted 25 July 1997 )
The high resolution f ar infrared absorption spectrum of IBr was recorded with a Fourier
transform spectrometer. The f undam ental 1 0 vibration rotation band and the 2 1 and 3 2
-1
hot bands were recorded at a resolution of 0 . 001 25 cm . The inf rared continuum was provided by synchrotron radiation emission f rom the Max-I storage ring. For high resolution
-1
spectroscopy at 250 cm synchrotron radiation is about 5 times brighter than a conventional
infrared glower. This increase in ux at the detector resulted in a corresponding increase in the
signal-to-noise ratio and a much improved inf rared spectrum.

1.

Introduction

The halogen and interhalogen molecules continue to

be extensively studied species. We recently recorded a
far infrared absorption spectrum of IBr [1] thus completing the spectrosc opic studies of interhalogen molecules in the infrared (IF [2], ICl [3], IBr [1], BrCl [4, 5],
BrF [5 7], ClF [7]) . The previous IBr paper [1] reviewed
the IBr spectrosc opic literature prior to 1993. Since then
additional papers have appeared, for example, the ana3
1
lyses of the A P 1 X S + system [8, 9], some vacuum
ultraviolet transitions [10, 11] and a number of UV tran3
3
sitions connecting to the A P 1 and A P 2 states [12
14]. Even an investigation concerned with the femtose3
cond wavepacket dynamics in the B P 0+ state of IBr has
also been reported [15].
Shortly after our conventional far infrared spectrum
of IBr was published [1], new spectra were recorded at
Lund using a storage ring as the source of continuum
radiation. These new spectra have an improved resolution and a higher signal-to-noise ratio because of the
higher brightness achievable with such a source. the
virtues of synchrotron radiation are well known for

Present address: Universite

Libre de Bruxelles, Service de
Chimie Physique Mole culaire, CP 160/09, A v F. D. Roosevelt
50, B-1050 Bruxelles, Belgium.
0026 8976/98 $12 . 00

ultraviolet and X -ray spectrosc opy but are not generally

appreciated for infrared work [16, 17].
A typical storage ring like Max-I in Lund is substan2
tially brighter ( photons per cm per steradian ) than a
blackbody source at 1400 K in the far infrared region.
The e ective source temperature of synchrotron radiation emission in the far infrared can be in excess of
10 000 K, which is even brighter than the widely used
mercury arc lamp which has an e ective plasm a temperature of 2000 K. In addition the synchrotron radiation is emitted from nearly a point source, since the
diameter of the electron beam is less than about 1 mm.
Under the experim ental conditions used with the Bruker
IFS 120 H R Fourier transf orm spectrom eter at a resolu-1
-1
tion of 0 . 002 cm at 250 cm about 5 times more signal
is expected (and observed ) for the Max-I storage ring
than for a glower [16].
The factor of 5 improvem ent in brightness of the far
infrared continuum translates directly into a factor of 5
improvem ent in the signal-to-noise ratio, all else being
equal. A Fourier transf orm spectrom eter using a conventional blackbody rather than a synchrotron will thus
require a factor of 25 more time to record an equivalent
spectrum , since the signal-to-noise ratio improves only
with the square root of the number of scans. Early work
with synchrotron radiation sources did not provide such
1998 T aylor & Francis Ltd.

138

B. Nelander et al.

Figure 1.

A portion of the inf rared absorption spectrum of IBr.

dramatic improvements in far infrared perf ormance

because of electron beam motion. This random beam
motion causes uctuations in intensity at the detector
and creates excess noise in the interf erogram . Modern
storage rings, like M ax-I, however, are much more
stable and the expected gain in performance is achieved
in practice [16].

2.

Experimental

The far infrared spectrum of IBr was recorded at

Lund with a Bruker IFS 120 H R spectrom eter and the
Max-I electron storage ring. The IBr sam ple was contained in an evacuated 20 cm cell sealed with polyethylene windows at a total pressure of 0. 6 Torr. The beam
current in the Max-I storage ring was 95 140 mA and
the radiation passed through a K RS-5 window bef ore
entering the spectrom eter.
The Bruker spectrom eter was operated with a 4 mm
entrance aperture at a resolution of 0. 001 25 cm - 1 . A
6 m m mylar beam splitter was used along with a silicon
bolometer detector operated at 4 . 2 K. Eight scans were
co-added.
The absorption lines were measured using the PCDECOMP program developed by J. Brault and then

calibrated with residual water lines. The estimated pre1

cision of the measurem ents is 6 0 . 0001 cm - .

3.

Results and discussion

A typical section of the spectrum is presented in gure

1. The resolution is improved by a factor of 2. 5 and the
signal-to-noise ratio by a factor of more than 3 over the
previous measurem ents [1]. The improved signal-tonoise ratio allowed the 3 2 hot band to be measured
plus the 2 1 and 1 0 bands [1]. The measured line posi79
tions are reported in table 1 for I Br and table 2 for
81
I Br. The line assignm ents were made easily with the
previous spectroscopic constants [1].
In reducing the data of tables 1 and 2 to spectroscopic
constants, the microwave [18] and millimetre wave [19]
transitions were included. The pure rotation al lines were
corrected for the e ects of hyper ne structure, and they
are provided in table 3 for convenience. These lines were
included in all of our ts.
The lines of tables 1 3 were tted using the conventional Dunham expression [20]:
E vJ =

i
Y ij ( v + 12) J ( J + 1)

]j ,

( 1)

and the constants listed in table 4. These constants are

more than an order of magnitude more precise than

139

High resolution far IR spectroscopy of IBr

Table 1.

79

I Br inf rared transitions (in cm

Line

Observed

Line

Observed

P( 111 )
P( 103 )
P( 98 )
P( 92 )
P( 88 )
P( 72 )
P( 67 )
P( 63 )
P( 59 )
P( 55 )
P( 51 )
P( 47 )
P( 43 )
P( 39 )
P( 35 )
P( 31 )
P( 27 )
P( 23 )
P( 19 )
P( 15 )
P( 11 )
P( 5)
R(10 )
R(14 )
R(18 )
R(22 )
R(26 )
R(30 )
R(34 )
R(38 )
R(42 )
R(46 )
R(50 )
R(54 )
R(58 )
R(62 )
R(66 )
R(70 )
R(74 )
R(78 )
R(82 )
R(86 )
R(90 )
R(94 )
R(98 )
R(102 )
R(106 )
R(110 )

252 . 081 08
253 . 316 56
254 . 076 21
254 . 975 87
255 . 568 07
257 . 875 99
258 . 577 30
259 . 131 31
259 . 679 30
260 . 221 12
260 . 756 91
261 . 286 50
261 . 809 96
262 . 327 17
262 . 838 15
263 . 342 95
263 . 841 54
264 . 333 92
264 . 820 07
265 . 299 92
265 . 773 47
266 . 471 44
268 . 265 22
268 . 697 68
269 . 123 75
269 . 543 30
269 . 956 69
270 . 363 25
270 . 763 52
271 . 157 36
271 . 544 66
271 . 925 39
272 . 299 66
272 . 667 31
273 . 028 44
273 . 382 95
237 . 730 84
274 . 072 07
274 . 406 72
274 . 734 69
275 . 055 83
275 . 370 18
275 . 678 06
275 . 979 05
276 . 273 27
276 . 560 63
276 . 840 91
277 . 114 66

26
15
- 21
- 10
- 4
- 1
6
- 4
- 4
- 8
- 1
1
8
8
4
3
3
5
8
7
4
- 55
- 3
0
5
0
19
1
0
5
5
0
3
0
2
2
1
0
4
10
3
- 10
3
5
9
9
- 14
- 4

P(108 )
P(102 )
P(97 )
P(91 )
P(87 )
P(71 )
P(66 )
P(62 )
P(58 )
P(54 )
P(50 )
P(46 )
P(42 )
P(38 )
P(34 )
P(30 )
P(26 )
P(22 )
P(18 )
P(14 )
P(10 )
R(6)
R(11 )
R(15 )
R(19 )
R(23 )
R(27 )
R(31 )
R(35 )
R(39 )
R(43 )
R(47 )
R(51 )
R(55 )
R(59 )
R(63 )
R(67 )
R(71 )
R(75 )
R(79 )
R(83 )
R(87 )
R(91 )
R(95 )
R(99 )
R(103 )
R(107 )

252 . 547 00
253 . 469 12
254 . 227 45
255 . 124 39
255 . 714 95
258 . 017 00
258 . 716 33
259 . 268 91
259 . 815 35
260 . 355 70
260 . 889 95
261 . 417 98
261 . 939 75
262 . 455 40
262 . 964 83
263 . 468 22
263 . 965 22
264 . 45603
264 . 940 56
265 . 418 80
265 . 890 92
267 . 826 53
268 . 373 89
268 . 804 56
269 . 229 22
269 . 647 24
270 . 058 78
270 . 463 93
270 . 862 51
271 . 254 75
271 . 640 47
272 . 019 59
272 . 392 37
272 . 758 42
273 . 117 67
273 . 470 51
273 . 816 77
274 . 156 43
274 . 489 27
274 . 815 46
275 . 135 04
275 . 447 92
275 . 753 88
276 . 053 25
276 . 345 72
276 . 631 22
276 . 909 93

(1, 0 ) Band
1
P(105 )
P(101 )
- 4
15
P(96 )
P(90 )
- 18
P(86 )
- 25
P(69 )
- 1
0
P(65 )
P(61 )
- 1
P(57 )
- 3
P(53 )
- 1
6
P(49 )
7
P(45 )
0
P(41 )
P(37 )
- 2
P(33 )
- 5
7
P(29 )
3
P(25 )
4
P(21 )
1
P(17 )
P(13 )
- 2
8
P(9 )
6
R(7 )
R(12 )
- 6
R(16 )
- 21
2
R(20 )
3
R(24 )
0
R(28 )
2
R(32 )
R(36 )
- 5
0
R(40 )
5
R(44 )
3
R(48 )
20
R(52 )
21
R(56 )
0
R(60 )
R(64 )
- 1
1
R(68 )
8
R(72 )
0
R(76 )
R(80 )
- 5
R(84 )
- 1
6
R(88 )
R(92 )
- 2
7
R(96 )
6
R(100 )
R(104 )
- 8
R(108 )
- 17

253 . 008 71
253 . 621 63
254 . 378 03
255 . 272 79
255 . 861 88
258 . 297 97
258 . 855 08
259 . 406 15
259 . 951 07
260 . 489 77
261 . 022 54
261 . 548 99
262 . 069 27
262 . 583 41
263 . 091 29
263 . 593 03
264 . 088 44
264 . 577 74
265 . 060 63
265 . 537 41
266 . 007 76
267 . 936 71
268 . 482 30
268 . 911 63
269 . 334 30
269 . 750 65
270 . 160 88
270 . 564 20
270 . 961 23
271 . 351 48
271 . 735 86
272 . 113 26
272 . 484 32
272 . 848 71
273 . 206 54
263 . 557 68
273 . 902 43
274 . 240 24
274 . 571 43
274 . 895 84
275 . 213 95
275 . 525 12
275 . 829 38
276 . 127 04
276 . 417 65
276 . 701 81
276 . 978 65

P( 107 )
P( 97 )
P( 85 )
P( 78 )

251 . 087 18
252 . 611 07
254 . 389 14
255 . 401 19

P(104 )
P(96 )
P(81 )
P(77 )

215 . 548 71
252 . 761 44
254 . 969 72
255 . 544 45

(2, 1 ) Band
29
P(101 )
18
P(92 )
P(80 )
- 9
16
P(76 )

252 . 006 17
253 . 358 69
255 . 113 97
255 . 686 80

17
9
- 10
- 4

Line

- 1) a

Observed

Line

Observed

105
8
24
- 1
- 3
8
2
3
2
- 6
6
4
1
4
0
3
- 2
3
- 7
0
- 9
- 4
3
14
0
- 5
21
1
1
- 28
5
- 6
3
2
4
- 2
15
3
- 3
- 19
6
12
2
11
- 5
16
- 8

P( 104 )
P( 100 )
P( 95 )
P( 89 )
P( 85 )
P( 68 )
P( 64 )
P( 60 )
P( 56 )
P( 52 )
P( 48 )
P( 44 )
P( 40 )
P( 36 )
P( 32 )
P( 28 )
P( 24 )
P( 20 )
P( 16 )
P( 12 )
P( 7 )
R(8 )
R(13 )
R(17 )
R(21 )
R(25 )
R(29 )
R(33 )
R(37 )
R(41 )
R(45 )
R(49 )
R(53 )
R(57 )
R(61 )
R(65 )
R(69 )
R(73 )
R(77 )
T(81 )
R(85 )
R(89 )
R(93 )
R(97 )
R(101 )
R(105 )
R(109 )

253 . 163 18
253 . 764 13
254 . 527 87
255 . 420 63
256 . 008 09
258 . 437 82
258 . 993 46
259 . 542 85
260 . 086 31
260 . 623 53
261 . 154 69
261 . 679 59
262 . 198 27
262 . 710 92
263 . 217 50
263 . 717 44
264 . 211 35
264 . 699 12
265 . 180 56
265 . 655 85
266 . 240 11
268 . 046 64
268 . 590 08
269 . 017 81
269 . 439 06
269 . 853 78
270 . 262 14
270 . 664 05
261 . 059 49
271 . 448 47
271 . 830 86
272 . 206 71
272 . 576 00
272 . 938 75
273 . 294 97
273 . 644 47
273 . 987 54
274 . 323 72
274 . 653 29
274 . 976 16
275 . 292 40
275 . 601 72
275 . 904 39
276 . 200 24
276 . 489 30
276 . 771 53
277 . 046 72

9
11
- 3
- 14

P( 98 )
P( 87 )
P( 79 )
P( 75 )

252 . 460 21
- 11
254 . 096 50
- 17
255 . 257 63
- 18
255 . 829 29
6
(continued )

9
942
- 2
- 1
- 15
6
6
- 7
0
- 3
2
- 1
- 9
- 1
20
0
- 1
7
9
23
- 59
- 1
- 8
2
5
- 1
- 1
0
2
7
5
3
0
0
5
0
15
7
5
3
10
0
0
- 3
- 3
- 3
- 21

140

B. Nelander et al.
Table 1.

Line

Observed

P( 74 )
P( 56 )
P( 52 )
P( 48 )
P( 44 )
P( 39 )
P( 35 )
P( 31 )
P( 27 )
P( 23 )
P( 19 )
P( 15 )
P( 11 )
R(16 )
R(20 )
R(24 )
R(28 )
R(32 )
R(36 )
R(40 )
R(44 )
R(48 )
R(52 )
R(57 )
R(61 )
R(65 )
R(69 )
R(73 )
R(77 )
R(81 )

255 . 971 13
258 . 459 58
258 . 995 79
259 . 525 67
260 . 049 30
260 . 695 19
261 . 204 99
261 . 708 30
262 . 205 58
262 . 696 60
263 . 181 08
263 . 659 71
264 . 131 69
267 . 258 37
267 . 679 66
268 . 094 25
268 . 502 42
268 . 904 07
269 . 299 27
269 . 688 03
270 . 070 10
270 . 445 62
270 . 814 62
271 . 266 60
271 . 620 66
271 . 968 17
272 . 308 71
272 . 643 15
272 . 970 68
273 . 291 29

P( 78 )
P( 53 )
P( 42 )
P( 29 )
P( 24 )
P( 15 )
R(27 )
R(33 )
R(39 )
R(51 )
R(65 )

253 . 773 62
257 . 226 08
258 . 669 18
260 . 314 31
260 . 928 69
262 . 010 83
266 . 734 52
267 . 335 40
267 . 919 59
269 . 045 28
270 . 282 93

Line

Observed

1
7
6
5
0
0
8
- 7
- 1
4
- 16
7
- 3
- 15
4
0
0
- 4
- 3
6
1
- 2
- 1
1
- 2
1
- 23
9
22
16

P(73 )
P(55 )
P(51 )
P(47 )
P(43 )
P(38 )
P(34 )
P(30 )
P(26 )
P(22 )
P(18 )
P(14 )
R(13 )
R(17 )
R(21 )
R(25 )
R(29 )
R(33 )
R(37 )
R(41 )
R(45 )
R(49 )
R(53 )
R(58 )
R(62 )
R(66 )
R(70 )
R(74 )
R(78 )
R(87 )

256 . 113 22
258 . 594 31
259 . 128 78
259 . 657 13
260 . 179 18
260 . 823 10
261 . 331 11
261 . 833 17
262 . 328 95
262 . 818 27
263 . 301 54
263 . 778 46
266 . 938 38
267 . 364 36
267 . 783 98
268 . 196 85
268 . 603 47
269 . 003 02
269 . 397 03
269 . 784 11
270 . 155 34
270 . 538 53
270 . 905 82
271 . 355 78
271 . 708 23
272 . 053 94
272 . 392 37
272 . 725 48
273 . 051 45
273 . 759 62

146
- 23
- 26
26
- 27
- 11
- 10
99
11
5
- 24

P(66 )
P(52 )
P(41 )
P(27 )
P(23 )
P(14 )
R(28 )
R(36 )
R(40 )
R(52 )
R(67 )

255 . 460 29
257 . 359 35
258 . 798 27
260 . 561 41
261 . 050 76
262 . 129 05
266 . 835 64
267 . 628 80
268 . 015 64
269 . 136 19
270 . 453 58

Continued.
Line

Observed

P(74 )
P(54 )
P(50 )
P(46 )
P(42 )
P(37 )
P(33 )
P(29 )
P(25 )
P(21 )
P(17 )
P(13 )
R(14 )
R(18 )
R(22 )
R(26 )
R(30 )
R(34 )
R(38 )
R(42 )
R(46 )
R(50 )
R(54 )
R(59 )
R(63 )
R(67 )
R(71 )
R(75 )
R(79 )
R(88 )

256 . 253 72
258 . 728 35
259 . 261 44
259 . 788 24
260 . 308 83
260 . 950 88
261 . 457 48
261 . 957 85
262 . 451 63
262 . 939 70
263 . 421 19
263 . 896 49
267 . 045 38
267 . 469 79
267 . 887 76
268 . 299 10
268 . 704 13
269 . 102 55
269 . 494 42
269 . 879 78
270 . 258 82
270 . 631 10
270 . 996 75
271 . 444 52
271 . 795 24
272 . 139 34
272 . 476 99
272 . 807 89
273 . 131 78
273 . 836 05

(3, 2 ) Band
3
P(63 )
P(44 )
- 10
P(31 )
- 3
19
P(26 )
0
P(22 )
R(25 )
- 13
3
R(26 )
1
R(37 )
8
R(44 )
R(53 )
- 15
22
R(68 )

255 . 873 36
258 . 410 51
260 . 065 40
260 . 683 99
261 . 172 33
266 . 531 56
266 . 936 25
267 . 726 01
268 . 395 67
269 . 227 26
270 . 538 53

d
58
5
0
1
- 8
- 10
- 24
- 9
2
- 4
10
20
- 10
- 4
9
- 5
1
- 50
- 4
0
- 925
1
- 2
5
5
- 3
- 73
- 5
19
15

Observed - calculated di erences (columns labelled d ) are in units of 0. 000 01 cm

those reported in [1] and comparable with those of [8].

A ppadoo et al. [8] used the new vibration rotation lines
reported here in a much more extensive t of the A 3 P 1
X 1 S + transition.
79
81
The I Br and I Br lines can be tted together using
the mass-independent Dunham expression [21, 22]

Line

Observed

4
11
0
0
0
5
6
8
- 23
1
- 3
1
- 19
- 8
1
- 5
4
2
- 2
- 6
13
13
9
5
- 1
- 4
15
29
14
1

P( 57 )
P( 53 )
P( 49 )
P( 45 )
P( 41 )
P( 36 )
P( 32 )
P( 28 )
P( 24 )
P( 20 )
P( 16 )
P( 12 )
R(15 )
R(19 )
R(23 )
R(27 )
R(31 )
R(35 )
R(39 )
R(43 )
R(47 )
R(51 )
R(55 )
R(60 )
R(64 )
R(68 )
R(72 )
R(76 )
R(80 )
R(91 )

258 . 324 60
258 . 862 16
259 . 393 78
259 . 919 05
260 . 437 96
261 . 078 07
261 . 583 09
262 . 081 96
262 . 574 47
263 . 060 66
263 . 540 62
264 . 014 30
267 . 152 33
267 . 574 95
267 . 991 13
268 . 401 09
268 . 804 56
269 . 201 16
269 . 591 37
269 . 975 18
270 . 352 34
270 . 723 11
271 . 086 97
271 . 532 74
271 . 881 98
272 . 224 49
272 . 560 20
272 . 889 30
273 . 211 52
274 . 063 36

P( 62 )
P( 43 )
P( 30 )
P( 25 )
P( 18 )
R(26 )
R(31 )
R(38 )
R(48 )
R(54 )

256 . 010 58
258 . 540 22
260 . 190 31
260 . 807 09
261 . 653 63
266 . 633 44
267 . 136 25
267 . 823 13
268 . 769 59
269 . 317 29

25
5
3
- 20
16
12
6
- 8
- 7
19
72

7
12
5
8
- 4
1
0
8
6
0
- 1
0
7
0
- 7
9
25
4
- 4
0
- 3
10
- 7
- 4
7
11
4
6
- 7
15

4
1
39
31
- 20
20
14
14
23
- 7

- 1.

E vJ =

U ij

i /2 + j

( v + 12) i J ( J + 1) j .

( 2)

The mass dependence of the Y ij constants has been

factored out explicitly in equation (2) , assuming the
Born Oppenheimer approximation. In our new com-

141

High resolution far IR spectroscopy of IBr

Table 2.
Line

Observed

P( 111 )
P( 106 )
P( 102 )
P( 98 )
P( 94 )
P( 90 )
P( 86 )
P( 81 )
P( 77 )
P( 73 )
P( 63 )
P( 56 )
P( 52 )
P( 48 )
P( 44 )
P( 40 )
P( 36 )
P( 32 )
P( 28 )
P( 24 )
P( 20 )
P( 15 )
P( 11 )
R(6 )
R(11 )
R(15 )
R(19 )
R(23 )
R(29 )
R(33 )
R(37 )
R(41 )
R(45 )
R(49 )
R(53 )
R(57 )
R(62 )
R(67 )
R(71 )
R(75 )
R(79 )
R(84 )
R(88 )
R(92 )
R(97 )
P( 98 )
P( 92 )
P( 87 )
P( 81 )
P( 77 )
P( 71 )
P( 67 )

81

I Br inf rared transitions (in cm

Line

Observed

250 . 297 90
251 . 059 74
251 . 662 49
252 . 259 31
252 . 850 12
253 . 435 27
254 . 014 38
254 . 730 13
255 . 295 95
255 . 855 77
257 . 229 05
258 . 168 16
258 . 697 10
259 . 219 50
259 . 735 89
260 . 246 20
260 . 750 60
261 . 248 85
261 . 741 06
262 . 227 09
262 . 707 20
263 . 298 58
263 . 764 92
265 . 786 22
266 . 326 01
266 . 750 57
267 . 168 47
267 . 580 53
268 . 186 06
268 . 582 82
268 . 972 59
269 . 355 71
269 . 733 17
270 . 103 94
270 . 468 33
270 . 826 27
271 . 264 55
271 . 692 84
272 . 028 17
272 . 357 09
272 . 679 34
273 . 072 91
273 . 380 44
273 . 682 08
274 . 048 12

4
5
3
- 1
- 18
- 9
- 14
0
2
- 1
- 27
- 40
7
3
0
- 6
0
- 1
0
- 7
2
0
12
- 32
15
27
- 1
11
- 44
13
4
- 33
- 1
- 1
1
2
- 6
- 4
- 2
8
6
1
4
78
1

P(110 )
P(105 )
P(101 )
P(97 )
P(93 )
P(89 )
P(85 )
P(80 )
P(76 )
P(72 )
P(62 )
P(55 )
P(51 )
P(47 )
P(43 )
P(39 )
P(35 )
P(31 )
P(27 )
P(23 )
P(19 )
P(14 )
P(10 )
R(7)
R(12 )
R(16 )
R(20 )
R(24 )
R(30 )
R(34 )
R(38 )
R(42 )
R(46 )
R(50 )
R(54 )
R(58 )
R(64 )
R(68 )
R(72 )
R(76 )
R(81 )
R(85 )
R(89 )
R(93 )
R(99 )

250 . 451 03
251 . 210 98
251 . 811 91
252 . 407 76
252 . 996 96
253 . 580 94
254 . 158 34
254 . 871 96
255 . 436 38
255 . 994 80
257 . 364 77
258 . 301 22
258 . 828 23
259 . 349 09
259 . 864 04
260 . 373 03
260 . 875 77
261 . 372 45
261 . 863 15
262 . 347 73
262 . 826 10
263 . 415 80
263 . 880 26
265 . 895 09
266 . 432 47
266 . 855 43
267 . 272 08
267 . 682 43
268 . 286 14
268 . 680 71
269 . 069 00
269 . 450 89
269 . 826 48
270 . 195 65
270 . 558 38
270 . 914 65
271 . 437 07
271 . 777 32
272 . 110 94
272 . 438 16
272 . 838 02
273 . 150 32
273 . 456 28
273 . 755 44
274 . 191 92

250 . 667 95
251 . 550 78
252 . 276 39
253 . 134 64
253 . 699 62
254 . 535 36
255 . 085 40

17
3
5
- 12
2
- 26
- 9

P(97 )
P(90 )
P(96 )
P(80 )
P(74 )
P(70 )
P(66 )

250 . 815 91
251 . 841 86
252 . 420 39
253 . 276 48
254 . 119 39
254 . 673 91
255 . 222 06

Observed

Line

Observed

(1, 0 ) Band
0
P(108 )
5
P(104 )
P(100 )
- 31
13
P(96 )
P(92 )
- 16
22
P(88 )
P(84 )
- 4
P(79 )
- 17
P(75 )
- 6
P(71 )
- 1
14
P(58 )
P(54 )
- 2
3
P(50 )
P(46 )
- 4
0
P(42 )
11
P(38 )
3
P(34 )
P(30 )
- 3
0
P(26 )
P(22 )
- 1
P(18 )
- 11
9
P(13 )
P(9 )
- 13
R(8 )
- 9
R(13 )
- 8
0
R(17 )
2
R(21 )
1
R(26 )
0
R(31 )
R(35 )
- 3
R(39 )
- 1
R(43 )
- 4
0
R(47 )
0
R(51 )
R(55 )
- 1
R(60 )
- 7
R(65 )
- 6
0
R(69 )
R(73 )
- 6
R(77 )
- 2
6
R(82 )
R(86 )
- 7
3
R(90 )
R(94 )
- 4
0
R(100 )

250 . 756 00
251 . 361 95
251 . 961 61
252 . 555 57
253 . 143 47
253 . 725 81
254 . 301 98
255 . 013 57
255 . 576 64
256 . 133 12
257 . 902 14
258 . 433 55
258 . 959 01
259 . 478 41
259 . 991 86
260 . 499 16
261 . 000 51
261 . 495 76
261 . 984 87
262 . 468 00
262 . 944 93
263 . 532 45
263 . 995 65
266 . 003 41
266 . 538 88
266 . 960 15
267 . 375 27
267 . 885 25
268 . 385 36
268 . 778 37
269 . 165 10
269 . 545 46
269 . 919 35
270 . 286 96
270 . 648 13
271 . 090 51
271 . 522 80
271 . 861 31
272 . 193 33
272 . 518 95
272 . 916 57
273 . 227 35
273 . 531 52
273 . 829 18
274 . 263 21

8
14
- 1
1
- 10
11
9
- 20
4
- 35
5
0
1
- 2
2
- 2
1
3
0
6
4
0
4
- 2
2
- 2
3
1
- 2
- 3
1
4
- 1
2
4
3
0
- 4
- 8
0
- 10
- 12
- 15
- 8
0

P( 107 )
P( 103 )
P( 99 )
P( 95 )
P( 91 )
P( 87 )
P( 82 )
P( 78 )
P( 74 )
P( 70 )
P( 57 )
P( 53 )
P( 49 )
P( 45 )
P( 41 )
P( 37 )
P( 33 )
P( 29 )
P( 25 )
P( 21 )
P( 17 )
P( 12 )
P( 8 )
R(9 )
R(14 )
R(18 )
R(22 )
R(27 )
R(32 )
R(36 )
R(40 )
R(44 )
R(48 )
R(52 )
R(56 )
R(61 )
R(66 )
R(70 )
R(74 )
R(78 )
R(83 )
R(87 )
R(61 )
R(96 )

250 . 908 24
251 . 512 20
252 . 110 80
252 . 703 04
253 . 289 67
253 . 870 34
254 . 587 64
255 . 155 15
255 . 716 49
256 . 272 16
258 . 035 44
258 . 565 46
259 . 089 40
259 . 607 29
260 . 119 13
260 . 615 23
261 . 124 91
261 . 618 60
262 . 106 18
262 . 587 79
263 . 063 19
263 . 648 84
264 . 110 50
266 . 111 20
266 . 644 75
267 . 064 48
267 . 478 01
267 . 986 07
268 . 484 25
268 . 875 76
269 . 260 75
269 . 639 46
270 . 011 80
270 . 377 82
270 . 737 38
271 . 177 52
271 . 608 02
271 . 944 98
272 . 275 40
272 . 599 39
272 . 995 06
273 . 304 06
273 . 606 70
273 . 975 60

17
11
13
- 7
1
4
- 10
11
11
39
- 7
- 1
- 2
- 5
- 10
- 985
4
1
- 3
4
2
2
6
- 9
- 2
- 4
- 1
1
1
8
- 1
- 4
- 5
0
1
- 22
- 1
0
- 1
7
6
- 8
0
2

(2, 1 ) Band
4
P(95 )
P(89 )
- 23
5
P(85 )
P(79 )
- 4
9
P(73 )
25
P(69 )
3
P(65 )

251 . 111 08
251 . 987 21
252 . 564 25
253 . 417 93
254 . 258 53
254 . 811 27
255 . 358 19

14
0
28
0
8
- 4
1

P( 93 )
P( 88 )
P( 82 )
P( 78 )
P( 72 )
P( 68 )
P( 64 )

251 . 404 51
0
252 . 132 06
9
252 . 992 61
- 1
253 . 558 92
- 2
254 . 397 30
7
254 . 948 50
- 8
255 . 493 75
- 20
(continued )

Line

- 1) a

142

B. Nelander et al.
Table 2.

Line

Observed

P( 63 )
P( 45 )
P( 40 )
P( 36 )
P( 32 )
P( 28 )
P( 23 )
P( 19 )
P( 14 )
P( 8 )
R(14 )
R(18 )
R(22 )
R(26 )
R(30 )
R(34 )
R(39 )
R(43 )
R(48 )
R(52 )
R(57 )
R(61 )
R(65 )
R(71 )
R(80 )

255 . 629 29
258 . 002 16
258 . 639 51
259 . 142 50
259 . 639 44
260 . 130 39
260 . 735 45
261 . 212 56
261 . 800 20
262 . 492 56
265 . 018 28
265 . 435 99
265 . 847 79
266 . 253 33
266 . 652 46
267 . 045 38
267 . 527 32
267 . 905 83
268 . 369 82
268 . 733 88
269 . 179 88
269 . 529 36
269 . 872 45
270 . 374 59
271 . 100 49

P( 84 )
P( 73 )
P( 58 )
P( 29 )
R(26 )
R(34 )
R(40 )
R(45 )
R(51 )
R(57 )
R(63 )

251 . 104 62
252 . 652 69
254 . 691 33
258 . 389 78
264 . 613 12
265 . 401 24
265 . 975 74
266 . 443 72
266 . 991 99
267 . 524 99
268 . 043 56

Observed

Line

Observed

6
0
- 2
- 9
- 11
- 2
5
8
2
- 13
30
- 6
- 4
1
0
11
0
4
- 3
0
3
1
9
- 5
2

P(62 )
P(43 )
P(39 )
P(35 )
P(31 )
P(27 )
P(22 )
P(17 )
P(13 )
R(9)
R(15 )
R(19 )
R(23 )
R(27 )
R(31 )
R(35 )
R(40 )
R(44 )
R(49 )
R(53 )
R(58 )
R(62 )
R(67 )
R(72 )
R(81 )

255 . 764 58
258 . 258 41
258 . 765 86
259 . 267 43
259 . 762 83
260 . 252 13
260 . 855 12
261 . 448 56
261 . 916 53
264 . 486 60
265 . 123 07
265 . 539 40
265 . 949 72
266 . 353 52
266 . 751 51
267 . 142 45
267 . 622 57
267 . 999 48
268 . 461 44
268 . 823 92
269 . 267 80
269 . 615 69
270 . 041 45
270 . 456 94
271 . 179 26

19
15
0
2
- 1
- 4
- 11
- 14
- 2
6
- 1
- 18
- 7
- 17
25
- 2
3
8
- 2
3
- 3
- 1
3
0
20

21
- 21
18
9
12
- 14
- 15
10
39
- 1
- 23

P(81 )
P(72 )
P(54 )
R(19 )
R(27 )
R(36 )
R(42 )
R(46 )
R(52 )
R(58 )
R(68 )

251 . 531 28
252 . 791 18
255 . 220 19
263 . 902 36
264 . 712 97
265 . 594 58
266 . 164 36
266 . 535 85
267 . 081 42
267 . 612 44
268 . 464 84

Continued.
Line

Observed

P(61 )
P(42 )
P(38 )
P(34 )
P(30 )
P(25 )
P(21 )
P(16 )
P(12 )
R(10 )
R(16 )
R(20 )
R(24 )
R(28 )
R(32 )
R(36 )
R(41 )
R(45 )
R(50 )
R(54 )
R(59 )
R(63 )
R(68 )
R(78 )
R(88 )

255 . 899 07
258 . 385 93
258 . 891 72
259 . 391 83
259 . 885 64
260 . 494 45
260 . 974 68
261 . 566 10
262 . 032 44
264 . 593 56
265 . 227 84
265 . 642 61
266 . 051 47
266 . 453 68
266 . 849 63
267 . 239 30
267 . 717 27
268 . 092 68
268 . 552 68
268 . 913 50
269 . 355 71
269 . 701 70
270 . 125 46
270 . 941 99
271 . 717 68

(3, 2 ) Band
5
P(75 )
P(68 )
- 24
P(53 )
- 11
5
R(20 )
3
R(31 )
9
R(37 )
17
R(43 )
R(47 )
- 10
R(54 )
- 9
R(59 )
- 4
R(70 )
- 4

252 . 374 53
253 . 341 42
255 . 351 52
264 . 004 94
265 . 108 95
265 . 690 34
266 . 257 61
266 . 627 91
267 . 260 08
267 . 699 68
268 . 630 39

calculated di erences (colum ns labelled d ) are in units of 0. 000 01 cm

bined ts no evidence for Born Oppenheimer breakdown could be detected.

The higher order U ij ( j > 1 ) are not independent constants but can be determ ined using relationships such as
U 02 =

4U 301
U 210

( 3)

that are implicit in the Dunham analysis [20 22]. We

have, theref ore, tted the data of tables 1 3 using equation (2 ) and these relationships to obtain a set of `constrained U ij parameters [23]. In this way the data set

Line

Observed

3
20
- 10
0
- 11
- 10
- 1
- 14
- 11
- 4
4
- 12
10
0
- 2
1
- 8
6
0
2
30
3
12
- 5
5

P( 60 )
P( 41 )
P( 37 )
P( 33 )
P( 29 )
P( 24 )
P( 20 )
P( 15 )
P( 11 )
R(13 )
R(17 )
R(21 )
R(25 )
R(29 )
R(33 )
R(38 )
R(42 )
R(47 )
R(51 )
R(56 )
R(60 )
R(64 )
R(70 )
R(79 )

256 . 033 44
258 . 512 65
259 . 017 37
259 . 515 81
260 . 008 14
260 . 615 49
261 . 093 82
261 . 683 45
262 . 147 99
264 . 912 20
265 . 331 91
265 . 745 57
266 . 152 46
266 . 553 40
266 . 947 68
267 . 431 85
267 . 811 76
268 . 277 91
268 . 643 44
269 . 091 48
269 . 442 59
269 . 787 25
270 . 291 93
271 . 021 35

P( 74 )
P( 64 )
P( 48 )
R(21 )
R(32 )
R(39 )
R(44 )
R(48 )
R(55 )
R(61 )
R(76 )

252 . 513 95
253 . 886 16
256 . 002 67
264 . 107 36
265 . 206 79
265 . 881 07
266 . 350 94
266 . 719 40
267 . 348 89
267 . 872 39
269 . 117 36

21
32
13
- 7
21
- 10
- 12
1
- 4
11
- 6

d
13
17
- 2
- 7
- 13
32
4
4
- 18
- 27
- 20
8
- 7
13
2
14
0
6
- 3
1
1
4
- 1
- 10

6
12
0
1
10
- 7
6
- 2
6
- 10
6

- 1.

(tables 1 3 ) could be reproduced by only 5 independent

U ij parameters (table 5 ) compared with the 18 conventional Dunham Y ij s (table 4 ) .
A n equally compact represen tation of the data was
obtained by tting the data directly to the eigenvalues
of the radial Schro dinger equation. In this case a modi ed Morse potential,
U ( z) = D e
with

[-

1 - e- b

e- b (

],
2

( z)
)

143

High resolution far IR spectroscopy of IBr

Iodine brom ide J

Table 3.
v

Observed

J + 1 pure rotational transitions (in cm

Observed

- 1)

Observed

Observed

2
78
43
52

0. 338 023 13
8. 943 843
4. 971 688
5. 965 622

36
1
0
1

0
0
1
2

43
79
52
61

4. 989 117
9. 056 535
5. 986 726
6. 976 004

2
71
62
62
62

0. 332 898 90
8. 030 651
7. 005 441
6.980 912
6. 906 597

28
1
0
- 1
- 30

0
0
1
2

44
80
71
71

5. 024 787
9. 030 063
8. 002 738
7. 974 687

79

0
0
0
1
3
0
0
1
2
3

2
52
87
61
61

0. 340 402 67
6. 007 731
9. 957 351
7. 000 707
6. 951 181

2
53
44
44
53

0. 335 224 97
6. 027 840
5. 007 367
4. 989 864
5. 964 800

28
1
- 1
0
- 4

1
0
0
1
4

11
0
1
1
0

0
0
1
2
4

2
61
95
79
61

0. 339 215 69
7. 025 289
10 . 856 779
9. 024 774
6. 926 234

I Br
0
2
0
- 1
1
- 4
0
2
- 12

2
62
53
53
53

0. 334 064 87
7. 029 852
6. 006 926
5. 985 914
5. 943 575

I 81 Br
0
0
0
1
12

0
0
1
2
5

Observed - calculated di erences ( colum ns labelled d ) are in units of 10

wave lines.
a

Table 4.

Mass-dependent Dunham constants ( in cm

79

Table 5.
U 10
U 20
U 30
U 01
2
10 U 11
3
10 U 21
5
10 U 02
7
10 U 12

).

cm

Table 6.

81

I Br
Y 10
Y 20
10 3 Y 30
2
10 Y 01
4
10 Y 11
10 7 Y 21
8
10 Y 02
11
10 Y 12
10 15 Y 03

-1

-8

I Br

268 . 681 076(37 )

- 0 . 816 597 6(216)
- 1 . 415 00( 375 )
5 . 683 255 33(103 )
- 1 . 969 037 4(650)
- 4 . 787 3(140 )
- 1 . 016 446(222)
- 5 . 081 3(425 )
- 1 . 678(166 )

266 . 627 934(37 )

- 0 . 804 123 4(210)
- 1 . 390 99( 361 )
5 . 596 734 74( 119 )
- 1 . 924 291 3(653)
- 4 . 641 2(122 )
- 0 . 986 162(275)
- 4 . 817 3(459 )
- 1 . 314(217 )

D e / cm

Re / A

for microwave lines and 10

-6

cm

0
0
1
1

0
1
2
1

f or millimetre

Derived parameter values f or the modi ed Morse

potential.

-1

14 660 . 0
2 . 468 985 985 7(437 )
9 . 308 343 015(796 )
17 . 902 504( 250 )
52 . 819 95(218 )
137 . 052(312 )
244 . 33( 190 )
126 . 904 473
78 . 918 336 1
80 . 916 289

M ( I) / u
79
M ( Br ) / u
81
M ( Br ) / u

Mass-independent Dunham constants (in cm - 1 ) .

1 874 . 207 68( 18 )
- 39. 733 494(738)
- 0. 482 374(899)
2. 765 405 45 ( 10 )
- 6. 684 324 4(893 )
1. 117 32( 204 )
- 2. 408 246 90
- 7. 765 773 86

10 U 22
10
10 U 03
10 11 U 13
15
10 U 04
15
10 U 14
19
10 U 05
23
10 U 06

9. 695 207 12
1. 531 544 01
4. 398 879 05
5. 335 113 31
2. 303 536 36
2. 231 700 26
1. 042 350 62

R - Re
z=
,
R + Re

b ( z) = z

i
b iz ,
i= 0

and

b (

) =

and the masses taken from Mills et al. [25]. This t

required 5 potential parameters ( b 0 b 4 ) and also led to
a new value for R e , the equilibrium bond length. The
utility of far infrared synchrotron radiation for high
resolution absorption spectroscopy is illustrated clearly
by our improved line positions and spectroscopic constants.
This work was supported by the National Sciences
and Engineering Research Council of Canada
(NSE RC ) . Partial support was also provided by the
Petroleum Research Fund, administered by the A merican Chemical Society. The infrared beam line was
nanced by grants from Knut and A lice W allenbergs
Stif telse and Forskningsra dsna mden. The stay of V.S.
in Lund was supported by a stipend from the Swedish
Institute.

i= 0

was used [23]. The potential param eters obtained in this

way are reported in table 6. The dissociation energy was
xed to the value quoted by Huber and Herzberg [24]

References

[1] C ampbell , J. M ., and B ernath, P. F., 1993, J. m olec.

S pectrosc., 158, 339.

144

High resolution far IR spectroscopy of IBr

[2] F rum, C. I., E ngleman, R ., and B ernath, P. F., 1990,

Chem . Phys. L ett., 167, 356.
[3] H edderich, H . G ., B ernath, P. F., and M c R ae, G . A .,
1992, J. m olec. Spectrosc., 155, 384.
[4] U ehara , H., K onno, T., O z aki, Y ., H oriai, K .,
N akagawa , K ., and J ohns, J. W . C., 1994, Can. J.
Phys., 72, 1145.
[5] N akagawa , K ., H oriai, K ., K onno, T., and
U ehara , H., 1988, J. m olec. S pectrosc. , 131, 233,
[6] B irk , H ., 1993, Z. Naturf ., 48a, 581.
[7] B u rger , H ., S chultz , P., J acob, E., and F a hnle, M .,
1986, Z. Naturf ., 41a, 1015.
[8] A ppadoo, D . R . T., B ernath, P. F., and LeR oy, R . J.,
1994, Can. J. Phys., 72, 1265.
[9] N ishimiya , N ., Y ukiya , T., and S uz uki, M ., 1995,
J. m olec. S pectrosc., 173, 8.
[10] Y encha , A . J., R idley, T., M aier, R ., F lood , R . V.,
L awley, K. P., D onovan, R . J., and H opkirk , A .,
1993, J. phys. Chem . , 97, 4582.
[11] K varan., A ., W ang , H ., and J ohannesson, G . H .,
1995, J. phys. Chem . , 99, 4451.
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