Rotational analysis of the ^3II_0(0^+)−^1Σ^+(0^+) system of indium iodide
11
Vol. 5, No. 10/October 1988/J. Opt. Soc. Am. B 1995 Rotational analysis of the 3Io(0+)-12+(O+) system of indium iodide Sumner P. Davis and Ruben Pecyner Department of Physics, University of California, Berkeley, Berkeley, California 94720 Received January 11, 1988; accepted May 27, 1988 The 3II-1+ band systems of InI were observed in both emission and absorption. Twenty new bandheads were observed. Rotational parameters for the 31Io(0+) state were determined from an analysis of seven bands. Vibra- tional parameters for the 3 1,1(1),fIIo(0+), and lI+(0+) states have been improved substantially. INTRODUCTION InI is a heavy molecule that presents a complex spectrum. The many rotational lines lying close together and the un- common structures of some of the bands and their mutual overlap make a challenging problem in spectral analysis and interpretation. Many bands have multiple heads that are clearly discernible, whereas in others the multiple heads are so close to one another that the bands are scarcelymore than broad intense lines with little or no structure. The earliest observations and vibrational analysis of the spectrum were reported by Wehrli and Miescher.1, 2 In addi- tion, Wehrli made a careful study of the behavior of relative band intensities and observed some bands of the 113In iso- tope. 34 Wehrli and Miescher observed and identified an extensive list of bandheads corresponding to two systems: A, A 3 Io (O+)-Xl'+(0+), and B, B 3 11l (1)-X '+ (0+). Bar- rett and Mandel 5 and Schenk et al. 6 obtained the rotational constants of the X 0+state from microwave spectroscopy. A rotational analysis for the A (0+)-X (0+) system was accomplished recently by Vempati and Jones. 7 They deter- mined origins for 11 bands, (0-0), (1-0), (1-1), (2-1), (2-2), (3-2)., (3-3), (4-3), (4-4), (5-4), and (5-5), and determined vibrational parameters of the A and X states. They mea- sured R-branch lines and from these calculated the rotation- al parameters for the A state. P-branch lines were not resolved. Our research was concentrated on measuring more accu- rately and completely the bandheads in both systems; on making rotational analyses using both P and R branches of eight bands in the A system, (0-0), (0-1), (1-0), (5-5), (5-7), (10-12), (10-14), and (12-14); on showing that some of the unusual features could be analyzed and explained; and on calculating vibrational and rotational parameters with in- creased accuracy and for higher vibrational levels. We re- tain the notations A and B for the excited states as given by Huber and Herzberg. 8 SOURCES The emission source was an electrodeless discharge lamp made of 9-mm fused-silica tubing 75 mm long. It contained approximately 20 mg of vacuum-distilled InI together with argon at a pressure of 1 Torr. The cell used for absorption consisted of a 15-mm silica tube 125 mm long, with a small sidearm. Flat polished quartz windowswere fused to both ends. The cell contained 50 mg of InI. It was heated with two electric ovens, one on each end, and was maintained at a temperature of 4000C. The vapor pressure was controlled by adjusting the tempera- ture of the sidearm with a separate heater. The continuum source was a tungsten halide lamp. SPECTROMETERS Emission spectra were recorded photographically on a 3-m Czerny-Turner spectrometer in the region from 22 600 to 25 000 cm-1 (443 to 400 nm). The plate factor was 1.7 cm-'/ mm (0.03 nm/mm), and the resolving limit was 0.040 cm-' (0.0007 nm). Wavelengths were measured by comparison with thorium lines emitted by an electrodeless discharge lamp. Kodak Type 103aO spectroscopic plates were used. Exposure times ranged from 30 sec to 3 h. Low-dispersion spectral observations were made from 300 to 925 nm, but no bands outside the region from 394 to 445 nm could be attrib- uted to InI. Absorption spectra were recorded digitally by using the Fourier-transform spectrometer at the Kitt Peak National Solar Observatory. Two sets of data were obtained at differ- ent temperatures of InI. One was at 3800C, and the other was at 2700C. Instrumental widths were 0.011 and 0.013 cm-', increased to 0.027 and 0.015 cm-', respectively, by the finite aperture size. The combined instrumental and Dopp- ler widths were 0.040 and 0.032 cm-'. A segment of the high-resolution spectrum is shown in Fig. 1. It shows the complex and blended character of the P head of the A system (0-0) band. The data were recorded in 4096-point records covering approximately 36 cm-' each. DATA REDUCTION The general data-processing code DECOMP developed at the National Optical Astronomy Observatories was used to pre- pare atlas plots and line lists. The 3800Crun yielded a list with 22,000 entries. In many regions the bands were satu- rated at this temperature, and a second list of 7000 entries covering these regions was prepared from the 2700Crun. 0740-3224/88/101995-11$02.00 © 1988Optical Society of America S. P. Davis and R. Pecyner
Transcript of Rotational analysis of the ^3II_0(0^+)−^1Σ^+(0^+) system of indium iodide
Vol. 5, No. 10/October 1988/J. Opt. Soc. Am. B 1995
Rotational analysis of the 3Io(0+)-12+(O+) system of indiumiodide
Sumner P. Davis and Ruben Pecyner
Department of Physics, University of California, Berkeley, Berkeley, California 94720
Received January 11, 1988; accepted May 27, 1988
The 3II-1+ band systems of InI were observed in both emission and absorption. Twenty new bandheads wereobserved. Rotational parameters for the 31Io(0+) state were determined from an analysis of seven bands. Vibra-tional parameters for the 31,1(1),fIIo(0+), and lI+(0+) states have been improved substantially.
INTRODUCTION
InI is a heavy molecule that presents a complex spectrum.The many rotational lines lying close together and the un-common structures of some of the bands and their mutualoverlap make a challenging problem in spectral analysis andinterpretation. Many bands have multiple heads that areclearly discernible, whereas in others the multiple heads areso close to one another that the bands are scarcely more thanbroad intense lines with little or no structure.
The earliest observations and vibrational analysis of thespectrum were reported by Wehrli and Miescher.1,2 In addi-tion, Wehrli made a careful study of the behavior of relativeband intensities and observed some bands of the 113In iso-tope.34 Wehrli and Miescher observed and identified anextensive list of bandheads corresponding to two systems:A, A3 Io (O+)-Xl'+(0+), and B, B311l (1)-X '+ (0+). Bar-rett and Mandel5 and Schenk et al.
6 obtained the rotationalconstants of the X 0+ state from microwave spectroscopy.
A rotational analysis for the A (0+)-X (0+) system wasaccomplished recently by Vempati and Jones.7 They deter-mined origins for 11 bands, (0-0), (1-0), (1-1), (2-1), (2-2),(3-2)., (3-3), (4-3), (4-4), (5-4), and (5-5), and determinedvibrational parameters of the A and X states. They mea-sured R-branch lines and from these calculated the rotation-al parameters for the A state. P-branch lines were notresolved.
Our research was concentrated on measuring more accu-rately and completely the bandheads in both systems; onmaking rotational analyses using both P and R branches ofeight bands in the A system, (0-0), (0-1), (1-0), (5-5), (5-7),(10-12), (10-14), and (12-14); on showing that some of theunusual features could be analyzed and explained; and oncalculating vibrational and rotational parameters with in-creased accuracy and for higher vibrational levels. We re-tain the notations A and B for the excited states as given byHuber and Herzberg.8
SOURCES
The emission source was an electrodeless discharge lampmade of 9-mm fused-silica tubing 75 mm long. It containedapproximately 20 mg of vacuum-distilled InI together withargon at a pressure of 1 Torr.
The cell used for absorption consisted of a 15-mm silicatube 125 mm long, with a small sidearm. Flat polishedquartz windows were fused to both ends. The cell contained50 mg of InI. It was heated with two electric ovens, one oneach end, and was maintained at a temperature of 4000C.The vapor pressure was controlled by adjusting the tempera-ture of the sidearm with a separate heater. The continuumsource was a tungsten halide lamp.
SPECTROMETERS
Emission spectra were recorded photographically on a 3-mCzerny-Turner spectrometer in the region from 22 600 to25 000 cm-1 (443 to 400 nm). The plate factor was 1.7 cm-'/mm (0.03 nm/mm), and the resolving limit was 0.040 cm-'(0.0007 nm). Wavelengths were measured by comparisonwith thorium lines emitted by an electrodeless dischargelamp. Kodak Type 103aO spectroscopic plates were used.Exposure times ranged from 30 sec to 3 h. Low-dispersionspectral observations were made from 300 to 925 nm, but nobands outside the region from 394 to 445 nm could be attrib-uted to InI.
Absorption spectra were recorded digitally by using theFourier-transform spectrometer at the Kitt Peak NationalSolar Observatory. Two sets of data were obtained at differ-ent temperatures of InI. One was at 3800C, and the otherwas at 2700C. Instrumental widths were 0.011 and 0.013cm-', increased to 0.027 and 0.015 cm-', respectively, by thefinite aperture size. The combined instrumental and Dopp-ler widths were 0.040 and 0.032 cm-'. A segment of thehigh-resolution spectrum is shown in Fig. 1. It shows thecomplex and blended character of the P head of the A system(0-0) band. The data were recorded in 4096-point recordscovering approximately 36 cm-' each.
DATA REDUCTION
The general data-processing code DECOMP developed at theNational Optical Astronomy Observatories was used to pre-pare atlas plots and line lists. The 3800C run yielded a listwith 22,000 entries. In many regions the bands were satu-rated at this temperature, and a second list of 7000 entriescovering these regions was prepared from the 2700C run.
0740-3224/88/101995-11$02.00 © 1988 Optical Society of America
S. P. Davis and R. Pecyner
1996 J. Opt. Soc. Am. B/Vol. 5, No. 10/October 1988
24368 24370 24372 24374 24376 24378 24380 24382 24384WAVE NUMBER (cm-)
24386 24388 24390 24392 24394 _4396WAVE NUMBER (cm )
24398 24400 24402
Fig. 1. Segment of the high-resolution absorption spectrum of InI. The P head of the A-system (0-0) band is shown at 24 392.10 cm-1.
SPECTRUM
The spectrum consists of two band systems that partiallyoverlap.2 4 They correspond to transitions from the A and Bexcited electronic states to the ground state. The A-systembands do not have Q branches, unlike the B-system bands,and they extend over a much larger wave-number regionthan do the B-system bands. There are 234 observableheads in the region 22 285-25 322 cm'; 134 belong to the Asystem, 67 to the B system, 3 assignments are ambiguous,and 30 are unassigned.
To characterize the band structures it is useful to useFortrat parabolas. Wave numbers of rotational lines in aband are commonly fitted by a polynomial function with arunning number m.9 The name parabola is retained eventhough the polynomial is often of degree greater than 2.The P and R branches can be connected together, and the Jnumbering and origin can be determined unambiguously ifm = -J for the P branch and m = J + 1 for the R branch.The Q branch is fitted with m = J. When these polynomialsare plotted they form Fortrat parabolas with an origin, a Qhead, and usually either a P or an R head. The formation ofheads depends on the values of the rotational parameters Iand higher-order terms in the rotational energy expression.InI is a special case because the molecule is a heavy one, the
values of B are small and nearly equal in the upper and lowerstates, and their differences change signs as the vibrationallevels change. For a single band we might observe both Pand R heads, as well as a Q head and subsidiary heads labeledP', Q', and R', for some of the three branches. In some casestwo P heads or two Q heads are formed close together in wavenumber, so that most of the band lines are contained be-tween the two heads. These bands look like broad lines orbars with sharply defined edges, and the heads are denotedby the subscript L. Also, there may be only an inflectionpoint on the parabola for a branch, which results in a diffusebump in the intensity. Such a feature is denoted by thesubscript M, for example, PM. The prime, M, and L nota-tions follow those of Wehrli and Miescher.1,2 All the ob-served bandheads are listed in Table 1. It includes 21 headsobserved by others but not by us.
VIBRATIONAL AND ROTATIONALPARAMETERS
We made rotational analyses of eight bands of system A,chosen so as to span a wide range of vibrational numbers.Their origins, because each was determined from fittingseveral hundred band lines of both the P and R branches,
0.8
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cn
0.6
0.4
0.2
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0
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Table 1. Bandheads of the Indium Iodide A and B Systemsa
System A System B
Sigma Observedb Measuredb Head v' u" Head v' u" Note
22 285.10 d d R 15 24
22 350.50 d d R 14 23
22 407.24 a a R 13 22
22 444.48 a,d a R 15 23
22 463.10 a a R 12 21
22497.21 a a22507.56 a a22 509.13 a a22 510.69 a,d a R 14 22
22 514.81 a a R 11 20
22 535.88 a a R 16 23
22557.49 a a R 10 19
22 571.46 a,d a R 13 21
22 607.49 a,d a R 15 22
22 627.20 a,d a R 12 20
22668.03 a a22 673.61 a,d a R 14 21
22 677.50 d d R 11 19
22 679.21 a a22714.86 a a22 725.58 a a R 10 18
22 734.64 a,d a R 13 20
22746.27 a a22751.78 a a22 770.09 a,d a R 15 21
22774.79 a a R 9 17
22 790.86 a,d a R 12 19
22836.50 a,d a R 14 20
22 842.61 a,d a R 11 18
22 890.98 a a R 10 17
22 897.63 a,d a R 13 19
22 954.68 a,d a R 12 18
23 000.05 a,d a R 14 19
23 007.15 a,d a R 11 17
23 056.23 a,d a R 10 16
23 062.01 a,d a R 13 18
23 102.75 a,d a R 9 15
23 119.34 a,d a R 12 17
23131.85 a a23 148.39 a,d a R 8 14
23 164.08 a,d a R 14 18
23 172.39 a,d a R 11 16
23 187.30 d d c
23 194.18 a a R 7 13 c
23209.58 a a23 221.53 a,d a R 10 15
23 223.39 a a23 226.82 a,d a R 13 17
23269.00 d d R 9 14
23 284.91 ab,c b R 12 16
23314.40 d d R 8 13
23 338.58 a,b,c b R 11 15
23 388.34 a,b,c b R 10 14
23 392.20 a,d a R 13 16
23 434.97 a,b,c b R 9 13
23 451.09 a,b,d b R 12 15
23 457.00 d d P 3 8
23 479.80 a,b,c b R 8 12
23 505.35 a,b,d b R 11 14
23 524.21 a,b,c b R 7 11
23 542.01 a,b,c b PL 6 10
23 542.20 b, b PL' 6 10
23 555.61 a,b,d b R 10 13(table continued)
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Table 1. ContinuedSystem A System B
Head v' v" Head v' v" Note
RRP
RP
R
PRPRRRPR*RPPRP
PMRPRP
PMRRPL
PLO*PLPL'RRPRPR
1365
15109
5 94 8
12 14
3 78 112 6
11 137 10
10 125 89 119 114 73 68 102 57 9
11 121 47 90 36 8
10 116 85 75 75 75 79 105 74 6
12 123 58 9
P 2 4R 11 11P 1 3R 7 8
P 0 2R 10 10R 6 7
PM 5 6R 9 9P 4 5
PR
PPR
3 48 8
2 31 27 7
R 4 8
Sigma
23 558.5623 568.9423 574.3523 581.5123 590.9423 602.8723 609.1523 614.8723 617.9323 622.9023 629.1623 647.4923 652.6023 672.8023 691.0323 723.6123 744.8523 767.3023 770.8723 774.5523 801.2423 815.4323 825.1923 835.0023 840.9223 846.6323 858.6223 865.7223 881.0023 892.3223 901.6523 913.3623 913.8123 915.8023 916.3523 940.0323 945.2323 946.4723 954.6223 973.9223 984.7423 989.8523 995.2123 998.6124 009.7124 020.7624 027.4224 035.8024 038.1024 040.5224 061.7124 069.9824 083.3924 087.6624 109.9424 118.9624 130.2024 147.2424 154.9524 162.8424 172.6724 195.5224 197.6124 205.5024 210.30
Observedb
a,b,da,da,b,c
aa,da,caa
a,b,ca
a,b,ca,dd
a,b,ca
a,b,ca,b,c
ca,b,ca,b,ca,b,ca,b,ca,b,c
cb,cb,c
a,b,cb,cb,c
a,b,ca,b,ca,b,c
ba,b,ca,b
a,b,ca,b,ca,b,ca,b,ca,b,ca,b,ca,c
a,b,ca,b,ca,c
a,b,ca,caa
a,b,ca,b,ca,ca
a,ca,b,ca,b,c
aa,b,ca,b,c
aa,b,ca,b,ca,b,c
aa
Measuredb
babaaaaababadbabbcbbbbbC
bbbbcbbbbbbbbbbbbaababaaabbaaabbabbabbbaa
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Table t. ContinuedSystem A System B
Observedb Measuredb Head vI u" Head v' v" Note
5 8
4 7
3 6 ee
PM 5 4R 5 4
PM 4 3
PM 4 2
2 5
5 75 7
1 4
4 64 6
QL 3 5
RPMQQ/
R
P
Q
P
pi
Q,
R
Q
QI
R
,
If
3 52 42 42 4
2 4
1 3.1 3
0 20 2? h
3 4?6 66 62 32 31 25 55 5
(table continued)
0665544434
1665544434
bcbbbbbbbbbbbabbbaa
PPMR
PMR
PL*PLPL'PR
RP
RPPR
8 72 2
7 61 10 06 5
R
R
R
R 9 7
Sigma
24 216.0224 225.0024 239.2224 259.0024 280.8024 291.2124 291.8624 292.5624 321.2724 323.0524 326.2224 329.5124 347.3824 366.8624 368.7324 370.9524 392.1524 409.7924 410.5224 411.1124 420.0024 450.5624 451.9424 454.7324 457.6024 465.1024 480.9024 483.0724 491.7124 495.6224 499.1924 506.1424 522.6824 529.4024 533.6624 536.8324 547.0324 573.70.24 577.0124 582.8724 609.0024 613.3024 618.7424 622.3024 623.9924 632.3624 640.0024 647.6224 650.8624 665.9724 670.4524 681.1024 691.6724 698.5724 713.7624 754.6224 770.8024 772.1124 787.6024 794.0724 821.7524 825.5024 827.42
R
a,b,cb,c
a,b,cb,c
a,b,ca,b
a,b,ca,b
a,b,ca,b,ca,b,ca,b,ca,b,c
aa,b,ca,b,ca,b,ca,b,c
aac
a,b,cb,caa
b,cc
a,ca,b,ca,b,ca,b,c
aa,b,c
ca,b,ca,b,ca,b,ca,b,c
aa,b,c
cc
a,b,ca
a,b,ca,cb,c
a,b,ca,b,c
aa,b,c
cb,c
a,b,ca,b,ca,b,cb,c
a,b,cc
a,b,ca,b,ca,b,ca,b,c
QR
R
QR
RPPI
P
P
4 33 23 2
2 1
1 0
R 10 7
R 5 3ababbaabcbbbbcbcbabb
PL
RPP'
3 1
3 1?2 02 0
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Table 1. ContinuedSystem A System B
Sigma Observedb Measuredb Head vI v" Head v' v" Note
24 832.80 c c R 8 4? Q' 1 2?24 856.63 b,c b P 0 124 858.70 c c Q 0 124 875.57 ab,c b Q 4 424 878.53 a,b,c b R 4 424 883.50 c c R 7 3? Q/ 0 1?24 921.08 ab,c b Q 3 324 926.83 a,b,c b R 3 324 958.00 b,c b PM 2 224 962.75 b,c b Q 2 224 963.54 a,b,c b Q/ 2 224 974.19 a,b,c b R 2 224 996.30 a,b,c b PM 1 125 000.56 a,b,c b Q 1 125 007.27 a,b,c b Q/ 1 125 022.06 ab,c b R 1 125 032.47 abc b P 0 025 034.76 a,b,c a Q 0 025 036.54 a,b,c a P' 0 025 053.12 a,b,c b QI 0 025 071.38 a,b,c b R 0 025 095.98 a,b,c b Q 3 225 100.50 ab,c b R 3 225 117.00 c c Q 6 425 118.35 ab,c b R 6 425 138.31 a,b,c b QL 2 125 138.64 b b QL* 2 125 147.08 a,b,c b R 2 125 170.00 b,c c PM 1 025 173.30 a,c a Q 5 325 174.83 a,b,c b R 5 325 176.83 ab,c b Q 1 025 180.31 a,b,c b Q/ 1 025 224.87 a,c a Q 4 225 226.80 ab,c b R 4 225 271.45 a,b,c a Q 3 125 275.13 a,b,c b R 3 125 314.50 ab,c a Q 2 025 321.59 a,b,c a R 2 0
a Units are inverse centimeters.b Key: a, grating spectra; b, Fourier-transform spectra; c, Ref. 2; d, Ref. 3; *, isotopic band; bold, identified by us.I Wehrli4 identified the 23 187.30-cm-1 transition as the R(7-13) head. He did not observe the 23 194.18-cm-1 transition, which fits better in the Deslandres
table.d Wehrli and Miescher2 questioned this identification, which we confirmed on the basis of our rotational analysis.I The accuracy of the table does not permit us to decide between the 24 411.11 and the 24 410.52-cm-' lines as the R(3-6) head.f These two identifications were made because the wave numbers fitted into the Deslandres table. The bands seem too intense for their positions in the table, and
neither one fits properly within the overall shape of the Condon parabola.g Wehrli and Miescher2 were uncertain about these identifications. They fit reasonably well and without ambiguity into our tables.h We found no evidence to help us to resolve this ambiguity, given by Wehrli and Miescher.2
i The head does not fit into the R(3-4) cell of the table.jWe do not observe either of these two heads and do not believe that they can be the R(8-4) and R(7-3) heads of system A. They do not fall within the Condon pa-
rabola. Moreover, the difference between their wave numbers is 51 cm', whereas the wave-number difference of other pairs of heads located nearby and having thesame relative positions is 41 cm-1 .
Table 2. Band Origins for the Indium Iodide Ahave small errors and were used to derive values for the Systemelecronic and vibrational parameters. lthe origins are givenin Table 2, and the electronic and vibrational parameters forall three states are given in Table 3. Those for the B statewere derived from our measurements of the Q heads and ouraccurate values for the parameters of the ground state.
The complexity of the spectrum required us to make acareful survey and selection of bands before making anyrotational analysis. The requirement was to find groups ofat least three reasonably intense bands with both P and Rbranches measurable and that have an upper and a lower
OriginBand (cm-')
(0-0) 24 393.3828 + 0.0010(1-0) 24 548.6253 i 0.0007(0-1) 24 217.117 + 0.0014(5-) 23 918.6482 I 0.0009
(10-12) 23 722.0598 .1 0.0026(10-14) 23 386.2497 + 0.0048(12-14) 23 617.1273 + 0.0032
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S. P. Davis and R. Pecyner ~~~~~~~Vol. 5, No. 10/October 1988/J. Opt. Soc. Am. B 2001
Table 3. Vibrational Parameters for the Indium Iodide X, A, and B Statesa
State Pe We WeXe WeYe
X 176.8251 ± 0.0036 .2752 + .0010 -. 002719 1 .000045A 24 403.1395 4- 0.0023 157.7898 + 0.0019 1.2148 ± .0011 -. 0362321d.000064B 25 051.02 ± 0.46 145.24 :1 0.54 1.58 1 .18 -. 077 .017
a Units are inverse centimeters.
level in common in order that combination differences couldbe calculated. Those satisfying these criteria were (0-0), (0-1), (1-0), and (10-12), (10-14), (12-14). Also, the (5-7)band was analyzed because it contains information corre-sponding to intermediate vibrational numbers and it pre-sents a PL feature. A profile of the band is shown in Fig. 2.Finally, the (5-5) band was examined in some detail to provethat the observed feature is actually part of a branch and isdue to an inflection point of the Fortrat parabola, but theresulting parameters were not considered accurate enoughto be used in the calculation of Be and ae. A comprehensivesmall-scale set of plots for all bands in the A system is shownin Fig. 3.
The general techniques of analysis are well known, 9 butthey can be quite tedious when applied to complex andseverely blended spectra. For analysis of the rotational
1
0.8
0.6
0.4
0.2
0
~~i I I I I I I I I - - F I I I I I I I I
-A -P (5-7)
spectrum, the interactive computer code ANALYSIS was spe-cially constructed by one of us' 0; it will be discussed inanother paper. Band lines were fitted with a polynomial,and lines differing in wave number by more than two stan-dard deviations from the fit were purged from the final fit.Our fitting extended to J = 255 in the (0-0) band, 208 in (0-1), 250 in (1-0), 227 in (5-5), 199 in (5-7), 218 in (10-1 2), and228 in (10-14). Final values of the rotational parameterswere calculated from a direct fit of all unpurged lines of aband instead of a separate fit of upper and lower rotationallevels uncoupled through combination differences. A wave-number list of lines in the (0-0) band is given in Table 4.
To gain a more quantitative understanding of the Pmfeatures, we analyzed the (5-5) band. An atlas plot is shownin Fig. 4. It has an R head at 24 281 cm-'. The strong andregularly spaced lines superposed onto the feature belong to
4- A - P (5-7)
13915 23916 23917 2q91 29923920WAVE NUMBER (cm)
0.8
0.6
0.4
0.2 I
0
23921 23922 23923WAVE NUMBER (cm-')
23924 23925
Fig. 2. High-resolution absorption spectrum of the PL feature of the A-system (5-7) band. The resolved structure in the larger-wave-numberregion shows the individual band lines.
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S. P. Davis and R. Pecyner
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o 0 1 2 3 4 5 6 7 8 9 10 11
0 _ _1 ZI ff f__ _ _ -_3~P IP r pp C R p
4
10SCX~~~~~~~~~~~~it~~iWAVE NUMBR >R R 8 __ a R 2R tR
WAVE NUMBER -Fig. 3. Fortrat parabolas for the A-system bands. Designations of the different features are explained in the text.
m
Table 4. Wave Numbers of Rotational Lines in the (0-0) Band of the A-X TransitionP() R() P() R() P(J) R(J)
J (cm-) (cm-') J (cm-') (cm-') J (cm-') (cm-')
64 24 393.121565 24 323.200566 24 393.263567 24 393.344268 24 393.409669 24 393.482270 24 393.558371 24 393.638372 24 393.714673 24 393.799474 24 393.890875 24 393.972776 24 394.062177 24 394.155278 24 394.250879 24 394.345680 24 394.446381 24 394.546982 24 394.642683 24 394.752584 24 394.860685 24 394.970086 24 395.079487 24 395.193588 24 395.300489 -90 24 395.543991 24 395.657492 24 395.776593 24 395.9085
24 402.896924 403.115924 403.333524 403.555524 403.773224 404.020424 404.242524 404.467124 404.687224 404.917824 405.165724 405.395324 405.641324 405.883824 406.126324 406.374524 406.624624 406.872224 407.130324 407.376824 407.628524 407.890924 408.155424 408.411024 408.681524 408.942824 409.207824 409.481024 409.757324 410.0300
949596979899
100101102103104105106107108109110111112113114115116117118119120121122123
24 396.027324 396.155224 396.286524 396.417924 396.550824 396.679224 396.813324 396.9571
24 397.2471
24 397.531224 397.680624 397.8372
24 399.119024 399.284224 399.457924 399.630724 399.800624 399.971624 400.153624 400.314324 400.5072
24 410.293924 410.574124 410.861624 411.138624 411.418824 411.708424 411.995824 412.289224 412.573724 412.864224 413.162724 413.465524 413.758224 414.063424 414.363024 414.672424 414.970124 415.278424 415.589324 415.897824 416.216724 416.521424 416.846324 417.158924 417.485024 417.800724 418.126824 418.452124 418.793124 419.1085
252733343839404142434445464748495051525354555657585960616263
24 392.1405
24 392.764024 392.8171
24 392.9422
24 396.071324 396.354624 397.2009
24 397.993724 398.145824 398.309024 398.465524 398.633024 398.802424 398.971724 399.169324 399.349924 399.523424 399.687624 399.887024 400.072124 400.260124 400.461524 400.640924 400.858924 401.045924 401.235024 401.434224 401.631024 401.831624 402.036224 402.251524 402.471824 402.6792
S. P. Davis and R. Pecyner
Vol. 5, No. 10/October 1988/J. Opt. Soc. Am. B 2003
J124125126127128129130131132133134135136137138139140141142143144145146147148149150151152153154155156157158159160161162163164165
P(J)(cm-')
24 400.6913
24 402.188124 402.409224 402.599824 402.800124 402.996924 403.205824 403.413524 403.621224 403.8281
24 405.328824 405.558324 405.777924 406.008224 406.218924 406.463124 406.6926
24 407.837924 408.080624 408.318324 408.564924 408.795024 409.035824 409.295724 409.5366
R(J)(cm-,)
24 419.429824 419.767724 420.103124 420.442824 420.773124 421.113824 421.445824 421.792424 422.139424 422.477924 422.834724 423.177224 423.524724 423.880324 424.232624 424.587724 424.931824 425.298524 425.660224 426.028724 426.377124 426.743324 426.111524 427.473724 427.843624 428.209024 428.595624 428.964024 428.334324 429.705424 430.087724 430.460424 430.842024 431.220024 431.611524 431.98022,4 432.366324 432.746424 433.138224 433.531024 433.919024 434.3124
Table 4. ContinuedP(J) R(J) P(J) R(J)
J (cm-) (cm-) J (cm'1) (cm-')
166167168169170171172173174175176177178179180181182183184185186187188189190191192193194195196197198199200201202203204205206207
24 410.510324 410.7796
24 411.273424 411.5464
24 434.692324 435.096524 435.493224 435.884924 436.278924 436.686224 437.073424 437.481724 437.873324 437.272224 438.679124 438.086724 439.496124 439.893324 440.301324 440.708124 441.130824 441.516424 441.945824 442.361224 442.763724 443.172624 443.592424 444.023924 444.421224 444.850924 445.281924 445.684124 446.105124 446.528624 446.950524 447.374724 447.784324 448.223824 448.642724 449.068524 449.496424 449.923024 450.341124 450.773824 451.203924 451.6334
208209210211212213214215216217218219220221222223224225226227228229230231232233234235242243244245246247248249250251252253254
24 452.061524 452.492024 452.923824 453.351224 453.784324 454.214624 454.649924 455.080824 455.513424 455.949024 456.380324 456.814924 457.248824 457.682524 458.115524 458.548624 458.981424 459.415824 459.852924 460.292224 460.727624 461.161124 461.594724 462.036624 462.461724 462.902424 463.340324 463.762524 466.809824 467.249324 467.690424 468.115024 468.546924 468.978024 469.417324 469.839624 470.259724 470.688624 471.129824 471.592224 471.9865
the (0-1) band, which forms a P head at 24 216 cm-'. Themain obstacle that we found in analyzing this band was thesubstantial number of unresolved lines within the featureitself: more than 70. There are also approximately 15 miss-ing lines near the origin. In spite of this, we obtained valuesof B5' and B5 ' consistent with the values predicted from theother bands.
The values of the parameters obtained from the rotationalanalyses of the seven bands are given in Table 5. Theequilibrium parameters are given in Tables 6 and 7. Fromthe latter parameters the equilibrium internuclear distancesre can be calculated. Their values are re(X) = 2.75314 ±0.00016 A and re(A) = 2.71078 + 0.00060 A. The errorsattached to the values presented in the tables were obtainedthrough a careful analysis, details of which are given byPecyner.10 One aspect of this analysis was the determina-tion of how many terms to include in the fits. The funda-
mental set of errors is, of course, the deviations of the lines ofeach band from the polynomial fit.
The vibrational number dependence of B is shown in Fig.5, which extends out to v' = 12 and clearly shows the crossingwith no extrapolation. Our values differ somewhat fromthose of Vempati and Jones7 because we were able to obtainexperimental values up to v' = 12 and v" = 14, well beyondthe crossover point.
To summarize, we note that for the X 1:(0+) state we havedetermined the rotational parameters from higher vibra-tional levels than previously observed and have calculatedthe vibrational parameters from band origins rather thanthe P heads. For the A 3IIo(0+) state we have determinedmore-accurate rotational parameters and calculated the vi-brational parameters from band origins. For the B 3ll(1)state we have determined vibrational constants by using ourmeasurements of the Q heads and by incorporating into the
. _ .
S. P. Davis and R. Pecyner
2004 J. Opt. Soc. Am. B/Vol. 5, No. 10/October 1988
0.8
zz
z
0.6
0.4
0.2
0
24255
0.8
v)zE-z
.-
0.6
0.4
0.2
0
24256 24257 2f258 24259 24260WAVE NUMBER (cm )
24261 24262 242q3 24264 24265WAVE NUMBER (cm )
Fig.4. High-resolution absorption spectrum of the PMfeature of the A-system (5-5) band. The wide and strong absorption lines belong to the(0-1) band. The narrower, more closely spaced and generally weaker lines belong to the (5-5) band. The head is at 24 258.17 cm 1 .
Table 5. Rotational Parameters for the Indium Iodide Xand A Statesav Bv' Error 108Dv' Error Band Bv" Error Bv"b 108Dv" Error Band
o .0379428 66 0.994 40 (0-0) .0368287 66 .0368149 0.744 40 (0-0)0 .0379422 92 1.119 50 (0-1) .0368255 40 0.737 21 (1-0)1 .0376922 40 1.016 21 (1-0) .0367192 92 .0367109 0.834 50 (0-1)5 .0365795 130 1.895 110 (5-7)7 .0360875 130 .0360862 1.431 110 (5-7)
10 .0347838 100 1.285 55 (10-12)10 .0347841 240 1.395 180 (10-14)12 .0339008 140 1.517 140 (12-14) .0355486 110 .0355657 0.395 57 (10-12)14 .0353329 240 .0353576 0.381 19 (10-14)14 .0353520 150 0.271 150 (12-14)
a Units are inverse centimeters.b Ref. 6.
Table 6. Equilibrium Rotational Parameters for the Xand A StatesBe ae 'Ye
State (cm-') (cm-') (cm-')
X 0.0368805 d 0.0000031 0.00010614 0.00000033A 0.038042 ± 0.000015 0.0002133 + 0.0000073 -0.00000938 0.00000055
S. P. Davis and R. Pecyner
Vol. 5, No. 10/October 1988/J. Opt. Soc. Am. B 2005
Table 7. Ground-State Rotational Parameters from References 5 and 6
Be ae YeSource (cm-') (cm-') (cm-')
Ref. 5 0.036857 ± 0.000015 0.00010397 + 0.00000050Ref. 6 0.0368670 + 0.0000005 0.00010411 + 0.00000020 0.00000008 + 0.00000002
0.038
0.037
0.036
0.035
0.034
0.033
Fig. 5.B,.
0 5 10 15
V
Vibrational number dependence of the rotational constant
calculation our precise values of the parameters of theground state.
ACKNOWLEDGMENTS
We gratefully acknowledge financial support from a Nation-al Science Foundation grant awarded to J. G. Phillips and S.P. Davis. We have had many helpful discussions with J. G.Phillips, R. J. Winkel, Jr., and J. W. Brault. The staff of KittPeak National Solar Observatory, especially J. Wagner andM. Brown, gave generously of their time to make the labora-tory observations successful.
S. P. Davis is a visiting astronomer, Kitt Peak NationalSolar Observatory, National Optical Astronomy Observa-tories, operated by the Association of Universities for Re-search in Astronomy, Inc., under contract with the NationalScience Foundation.
REFERENCES
1. M. Wehrli and E. Miescher, "Die Spektren der Indiumhalo-genide," Helv. Phys. Acta 6, 457 (1933).
2. M. Wehrli and E. Miescher, "Spektroskopische Untersuchungdampfformiger Indiumhalogenide," Helv. Phys. Acta 7, 298(1934).
3. M. Wehrli, "Das Indium Isotop 113," Helv. Phys. Acta 7, 611(1934).
4. M. Wehrli, "Das anormale Verhalten der Intensitat Im Banden-spektrum von Indiummonojodid," Helv. Phys. Acta 9, 587(1936).
5. A. H. Barrett and M. Mandel, "Microwave spectra of the Ti, In,and Ga monohalides," Phys. Rev. 109, 1572 (1958).
6. B. Schenk, E. Tiemann, and J. Hoeft, "Hyperfeinstruktur desRotationsspektrums bie zwei vergleichbaren Quadrupolkop-plungskonstanten: InJ," Z. Naturforsch. 25a, 1827 (1970).
7. S. N. Vempati and W. E. Jones, "The spectra and structure ofindium iodide: the rotational and vibrational constants of theAO+ state," J. Mol. Spectrosc. 120, 441 (1986).
8. K. P. Huber and G. Herzberg, Constants of Diatomic Molecules(Van Nostrand Reinhold, New York, 1979).
9. G. Herzberg, Spectra of Diatomic Molecules, 2d ed. (Van Nos-trand, Princeton, N.J., 1950).
10. R. Pecyner, Ph.D. dissertation (University of California, Berke-ley, Berkeley, Calif., 1986).
S. P. Davis and R. Pecyner
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