1659

The infrared emission spectra of LiF and HF

H. G. HEDDERICH.1 I. FRUM,R. ENGLEMAN, ANDP. F. BERNA11-Il C. JR..
Department of Chemistry, The University of Arizona, Tucson, AZ 85721. U.SA

Received Marcb 20. 1991 This paper is dedicated to Dr. Richard Norman Jones
H. O. HEODERlCH. 1. FRUM, . ENGLEMAN, and P. F. BERNATH. C. R JR_. Can. J. Cbem. 69, 1659 (1991). The high resolution infrared spectrum of LiF has been measured in emission with the McMath Fourier transform interferometer at Kitt Peak. A total of 800 lines with v = I --+ 0 to v ee 8 --+ 7 of the main isotopomer, 7LiF, and 250 lines with v = I --+ 0 to v = 3 ----> 2 of the minor isoropomer, 6LiF. were observed. These ro-vibrational transitions and the pure rotational transitions from the literature were fit to a set of Dunham coefficients Y ij and a set of mass-reduced Dunham coefficients Uii. The same spectrum shows 13 pure rotational emission transitions of HF in the vibrational ground state with J = 13 --+ 12 to J = 25 --+ 24. These transitions were used to determine an improved set of rotational constants for HF. Key words: infrared spectra. LiF, HF.

H. G. HEDDERICH. I. FRuM,R. ENGLEMAN, et P. F. BERNATH. C. JR. Can. J. Chern. 69, 1659 (1991). ; On a rnesure les spectres d'emission infrarouge 11haute resolution du LiF l'aide d'un inrerferometre 11transformation de McMath founer au ni veau Kin Peak. On a observe 800 raies avec des valeurs de v allant de v = I_,O v = 8 --+ 7 pour l'jsotopomere principal. 7LiF, et on a observe 250 raies avec des valeurs de valiant de v = I - 0 a v = 8 --+ 7 pour l'isotopomere minoritaire. On a adapte ces transitions de vibration-to et les transitions de rotation pure repertoriees dans la litterarure un ensemble de coefficients de Dunham Yij et un ensemble de coefficients Uij de masse reduite Dunham. Ces memes spectres montrent \3 transitions d'emission de rotation pure du HF dans I'etat fondamental de vibration avec J = 13 --t 12 Ii J = 25 --+ 24. On a utilise ces transitions pour determiner un ensemble ameliore de constantes de rotation pour

Ie HF.

Mots cles : spectres infrarouge, LiF, HF.

[Traduit par la redaction)

I. Introduction
The infrared spectra of alkali halides have been of interest to spectroscopists for a long time (1.2). However, high-resolution infrared data for these molecules have only become available after the introduction of diode laser and Fourier transform infrared spectrometers. Nevertheless. the first infrared data on LiF was obtained by Vidale (3) as early as 1959 with a PerkinElmer grating spectrometer. He observed the spectrum of LiF both in absorption and emission. However, the resolution was not high enough to obtain an unambiguous rotational assignment and, therefore, the correct band center. Vidale gave three possible assignments. Only after the microwave measurements on 6LiF by Wharton et al. (4) did the correct assignmenl become apparent. Several additional papers report the infrared spectrum of LiF trapped in low temperature matrices (5-10). The first high-resolution infrared data on Li.F was published by Maki (11). He used a tunable diode laser system for the observation of ro-vibrational transitions with v 1 +-- 0 to v = 8 +-- 7 for 7UF and 6LiF. Diode lasers display many gaps in their spectral coverage. Therefore, only a few lines of each vibrational band were accessible. In this paper the complete emission spectra of 7UF and 6LiF between 630 and 1030 cm"' are published (Figs. I. 2). HF is an important gas for use as an absolute wavenumber standard. In 1987 Jennings et al. (12) published rotational constants for HF calculated from measurements in four different laboratories. Highly accurate data in the far infrared (J = I <------ 0 to J = 4 <------ 3) were obtained with a tunable far-infrared spectrometer at the National Bureau of Standards laboratory in Boulder. Transitions with J = 5 <------ 4 to J = 7 <------ 6 were measured with a commercial high-resolution Fourier transform

spectrometer at the National Research Council, Ottawa, Canada. Lines with J = 17 to J = 21 were observed with a vacuum grating spectrograph (13) and lines with J = 26 to J = 32 with a tunable diode laser spectrometer at the University of Lille, France. In 1988 Jennings and Wells (14) remeasured the J = 27 <------ 26 and J = 33 <------ 32 transitions by using a tunable diode laser heterodyne spectrometer (15). Except for these two lines, the mid-infrared transitions are relatively inaccurate. Unfortunately the uncertainties in the molecular constants in this publication seem to be a factor of 10 too small. As a byproduct of our work with LiF. we publish thirteen rotational transitions of HF in the range 500 to 900 em-I. A new fit including the far-infrared data and the diode laser measurements provide an improved set of rotational constants for HF. II. Experimental The high resolution infrared emission spectra of 6LiF,'LiF, and HF between 500 and 1400 em"! were observed with the McMath Fourier transform spectrometer at Kitt Peak. The unapodized resolution was 0.0055 em"! with a liquid helium cooled As:Si detector and a KCI beamsplitter. The upper wavenumber limit was set by a wedged inSb filter while the lower limit was given by the transmission of the KCI beamsplitter and by the detector response. The spectrum of LiF was taken accidentally during an attempt to observe the infrared spectrum of MgFz. Solid MgFz was heated to about 1500 K in an alumina tube furnace. The apparatus used for the experiment was described in detail earlier (16). The heating rate was about 5 Klmin. The temperature of the furnace was measured with a chromel-alumel thermocouple placed between the healing elements and the alumina tube. Deposition of solid material onto the windows was avoided by pressurizing the cell with 5 Torr of argon. A series of spectra were taken as the furnace heated up and then cooled down. Initially a globar was placed behind the tube furnace and its image was focused on the 8 mm aperture of the Fourier transform spectrometer. No absorption spectra were observed, but when the globar was shut off (at a temperature of about 1300 K) an emission spectrum was monitored. The inlen-

1 Also affiliated with Centre for Molecular Beams and Laser Chemistry, Department of Chemistry, The University of Waterloo. Waterloo, Ont., Canada N2L 301. Priraed in Canada I lmprime au Canada

1660
TABLE

CAN. J. CHEM.

VOL. 69, 1991

1. Ro-vibrational transitions of 7LiF and 6LiF Obs. - calc. /10-5 cm " Obs. - calc. /10-5 cm-1 -16 -15 -16 -19 -10 -19 -23 -17 -21 -17 -18 -20 -16 -16 -16 -)7 -17 -13 -14 -16 -)8 -20 -12 -11 -)6 -11 -11 -5 -9 -8 -7 -5 -1 -3 1 -) 1 3 6 8 9 16 -42 13 I3 16 14 10 20 23 19 27 16 27 -41 20 26 -14 -11 -9 28 5 -28 -56

i"
7LiF

Obs./cm-1

i"
P4 P3 P2 PI RO Rl R2 R3 R4 R5 R6 R7 R8 RIO Rll R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R45 R46 R47 R48 R49 R50 R51 R52 R53 R54 R55 R58 R59 R60 R61 R62

Obs.rcm""
883.42268(50) 886.21112(50) 888.96043(50) 891.67033(50) 896.97099(50) 899.56097(50) 902.11051(50) 904.61936(50) 907.08707(50) 909.51355(50) 911.89840(50) 914.24140(50) 916.54237(50) 921.0)692(50) 923.19005(50) 925.32007(50) 927.40677(50) 929.44992(50) 931.44921(50) 933.40445(50) 935.31541(50) 937.18186(50) 939.00368(50) 940.78049(50) 942.51208(50) 944.19838(50) 945.83905(50) 947.43398(50) 948.98282(50) 950.48550(50) 851.94180(50) 953.35151(50) 954.71447(50) 956.03041(50) 957.29927(50) 958.52075(50) 959.69477(50) 960.82113(50) 961.89967(50) 962.93020(50) 963.91257(50) 964.84670(50) 965.73172(50) 966.56926(50) 967.35751(50) 968.09690(50) 968.78722(50) 969.42838(50) 970.02040(50) 970.56296(50) 971.05594(50) 971.49941(50) 971.89296(50) 972.23690(50) 972.53012(50) 972.77459(50) 972.96841(50) 973.11156(50) 973.20486(50) 973.18288(50) 973.07410(50) 972.91472(50) 972.70458(50) 972 .44380( 100)

v = 1~0

P67 P66 P65 P64 P63 P62 P61 P60 P59 P58 P57 P56 P55 P54 P53 P52 P51 P50 P49 P48 P47 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27 P26 P25 P24 P23 P22 P21 P20 P19 P18 P17 P16 P15 P14 P13 P12 Pl1 PIO P9 P8 P7 P6 P5

643.22499(50)U

647.79186(50) 652.34367( 100) 656.87691(50) 661.39365(50) 665.89322(50) 670.37521(50) 674.83778(50) 679.28310(50) 683.70808(50) 688.11522(150) 692.49965(50) 696.86537(50) 701.21006(50) 705.53328(50) 709.83535(50) 714.11486(50) 718.37200(50) 722.60630(50) 726.81744(50) 731.00488(50) 735.16819(50) 739.30720(50) 743.42133(50) 747.51018(50) 751.57345(50) 755.61069(50) 759.62154(50) 763.60582(50) 767.56266(50) 771.49217(50) 775.39382(50) 779.26714(50) 783.11189(50) 786.92762(50) 790.71410(50) 794.47076(50) 798.19745(50) 801.89368(50) 805.55917(50) 809.19351(50) 812.79639(50) 816.36742(50) 819.90638(50) 823.41278(50) 826.88635(50) 830.32668(50) 833.73363(50) 837.10660(50) 840.44548(50) 843.74986(50) 847.01934(50) 850.25377(50) 853.45267(50) 856.61580(50) 859.74286(50) 862.83347(50) 865.88735(50) 868.90424(50) 871.88380(50) 874.82572(50) 877. 73041 (50) 880.59549(50)

-32 -14 11 3 5 21 56 -20 52 60 130 -11 1 22 5 38 21 12 6 10 10 2 9 12 9 10 7 3 18 1 3 6 1 1 -4 1 -5 -3 -4 -3 -5 -5 -9 -4 -5 -4 -10 -3 -9 -8 -6 -7 -10 -11 -9 -11 -14 -14 -13 -13 57 -11

-11

HEDDERICH TABLE

ET AL.

1661

1 (continued) Obs. - calc. /10-5 cm-1 -17 -25 -32 17 -9 -11 -II -28 -21 -19 -20 -19 -19 -17 -17 -18 59 -16 -15 -16 -15 -13 -lO -16 -12 -13 -7 -6 -8 -9 -8 -5 1 -2 -1 0 2 0 21 .8 7 15 8 9 14 12 9 II 15 26 5 21 1 12 2 52 26 22 -6 -71 32 -8 69 47

J" R63 R64 R66 R67 P66 P65 P64 P63 P62 P61 P60 P59 P58 P57 P56 P55 P54 P53 P52 P51 P50 P49 P48 P47 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P29 P28 P27 P26 P25 P24 P23 P22 P2l P20 P19 P18 P17 P16 PI5 P13 P12 Pll PIO P9 P8 P7 P6 P5

Obs.j'cm"! 972 .13208( 1(0) 971.76979(150) 970.88707(1000) 631.22869(50) 635.72007(50) 640.19664(50) 644.65580(50) 649.09925(50) 653.52568(50) 657.93478(50) 662.32515(50) 666.69846(50) 671.05195(50) 675.38687(50) 679.70218(50) 683.99744(50) 688.27260(50) 692.52716(50) 696.76022(50) 700.97172(50) 705.16135(50) 709.32807(50) 713.47301(50) 717 .59424(50) 721.69209(50) 725.76575(50) 729.81524(50) 733.83991 (50) 737.83964(50) 741.81377(50) 745.76208(50) 749.68415(50) 753.57956(50) 757.44812(50) 761.28913(50) 765.10256(50) 768.88784(50) 772.64482(50) 776.37275(50) 780.07159(50) 787.38047(50) 790.98979(50) 794.56839(50) 798.11622(50) 801.63268(50) 805.11760(50) 808.57063(50) 811.99123(50) 815.37936(50) 818.73443(50) 822.05627(50) 825.34455(50) 828.59880(50) 831.81897(50) 835.00440(50) 841.27036(50) 844.35032(50) 847.39426(50) 850.40221(50) 853.37365(50) 856.30845(50) 859.20616(50) 862.06649(50) 864.88929(50)

Obs. - calc. /10-5 cm-1 -lO3 -131 -757 -31 -54 12 -49 -24 -2 30 -27 30 -10 -4 -7 -21 -9 18 12 6 11 -39 10 4 16 3 6 -1 8 5 7 7 3 13 2 5 2 14 1 -4 -3 1 -9 -4 -9 -8 -2 -10 -4 -9 -lO -6 -12 -1 -8 -12 -5 -17 -15 -21 -17 -18 -24 -20

J" P4 P3 P2 PI RO RI R2 R3 R4 R5 R6 R7 R8 R9 RlO RII R12 R13 R14 R15 R16 RI8 RI9 R20 R2l R22 R23 R24 R25 R26 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R45 R46 R47 R48 R49 R50 R51 R52 R53 R55 R58 R60 R61 R62 R63 P63

Obs.Zcm"! 867.67416(50) 870.42072(50) 873.12879(50) 875.79864(50) 881.01967(50) 883.57101(50) 886.08249(50) 888.55365(50) 890.98463(50) 893.37488(50) 895.72416(50) 898.03226(50) 900.29890(50) 902.52385(50) 904.70683(50) 906.84760(50) 908.94670(50) 911.00160(50) 913.01435(50) 914.98392(50) 916.91013(50) 920.63150(50) 922.42624(50) 924.17663(50) 925.88263(50) 927.54388(50) 929.16031(50) 930.73159(50) 932.25754(50) 933.73800(50) 935.17279(50) 936.56172(50) 937.90461(50) 939.20117(50) 940.45135(50) 941.65492(50) 942.81174(50) 943.92159(50) 944.98457(50) 945.99995(50) 946.96804(50) 947.88866(50) 948.76142(50) 949.58641(50) 950.36345(50) 951.09230(50) 951.77288(50) 952.40513(50) 952.98891(50) 953.52413(50) 954.01031(50) 954.44802(50) 954.83642(50) 955.17610(50) 955.46643(50) 955.70813(100) 955.89976(50) 956.13526(50) 956.11660(50) 955.85520(100) 955.65116(50) 955.39582(50) 955.09177(50) 637.08050(50)

v=2~1

v=3~2

1662

CAN. 1. CHEM. VOL. 69.1991 TABLE

I (continued) Obs. - calc. /10-5 cm " -9 27 15 -10 -II -10 -10 -8 -6 -8 -9 -7 -5 -6 -4 -6 -3 0 -2 -2 1 -2 -1 -2 3 5 7 7 5 10 12 5 12 14 24 12 4 9 18 8 6 -6 6 -4 -7 -3 26 II 44 58 -116 -1 -83 -35 -25 -38 -24 19 -156 -24 1 -27 -27 -10

J" P62 P61 P60 P59 P58 P57 P56 P55 P54 P53 P52 P51 P50 P49 P48 P47 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27 P25 P24 P23 P22 P21 P20 P19 P18 PI7 PI6 PI5 P14 P13 P12 Pll PlO P8 P7 P6 P5 P4 P3 P2 PI RO RI R2 R3

Obs.ycrn " 641.43448(50) 645.77142(50) 650.09061(50) 654.39259(50) 658.67705(50) 662.94016(100) 667.18712(50) 671.41350(50) 675.62027(50) 679.80640(50) 683.97197(50) 688.11522(100) 692.23944(50) 696.34045(50) 700.41927(50) 704.47535(50) 708.50834(50) 712.51815(50) 716.50367(50) 720.46523(50) 724.40076(150) 728.31423(50) 732.20075(50) 736.06160(50) 739.89648(50) 743.70475(50) 747.48629(50) 751.24050(50) 754.96726(50) 758.66554(50) 762.33658(50) 765.97844(50) 769.59128(50) 773.17489(50) 776.72871(50) 780.25263(50) 787.20868(50) 790.64043(50) 794.04065(50) 797.40920(50) 800.74569(50) 804.04978(50) 807.32117(50) 810 .55952(50) 813.76451(50) 816.93581(50) 820.07305(50) 823.17607(50) 826.24442(50) 829.27779(50) 832.27601(50) 835.23860(50) 841.05602(50) 843.91016(50) 846. 72833( 100) 849.50808(50) 852.25109(50) 854.95662(50) 857 .62348( 100) 860.25368(50) 865.39691(50) 867.90996(50) 870.38398(50) 872.81853(50)

Obs. - calc. /10-5 em"! 38 23 -26 -14 71 -114 -7 -10 14 4 6 -114 12 7 10 7 1 23 -1 1 -140 II 2 -I 9 4 II 4 8 -44 9 7 1 7 3 11 -3 4 -2 -3 -3 -4 -4 -4 -3 -3 -8 -5 -5 -10 -5 -9 -7 -11 62 -4 -II -6 -79 -I -1 -21 -18 -10 R4 R5 R6 R7 R8 R9 RIO RII RI2 RI3 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R45 R46 R47 R48 R49 R50 R51 R54 R55 R58 P61 P60 P59 P58 P57 P56 P55 P54 P53 P52 P51 P50 P49

J"

Obs.zcm"! 875.21320(50) 877.56817(50) 879.88235(50) 882.15584(50) 884.38874(50) 886.58060(50) 888.73113(50) 890.84013(50) 892.90734(50) 894.93247(50) 896.91535(50) 898.85576(50) 900.75346(50) 902.60817(50) 904.41976(50) 906.18792(50) 907.91254(50) 909.59335(50) 911.23010(50) 912.82266(50) 914.37083(50) 915.87433(50) 917.33306(50) 918.74679(50) 920.11539(50) 921.43861 (50) 922.71629(50) 923.94823(50) 925.13427(50) 926.27433(50) 927.36815(50) 928.41551(50) 929.41649(50) 930.37073(50) 931.27823(50) 932.13854(50) 932.95179(50) 933.71793(50) 934.43673(50) 935.10785(50) 935.73142(50) 936.30716(50) 936.83529(50) 937.31524(50) 937.74720(50) 938.13106(50) 938.46692(50) 938.75398(50) 939.32502(50) 939.41816(100) 939 .40280( 100) 633.87765(50) 638.12641(100) 642.35907(50) 646.57356(50) 650.76959(50) 654.94728(50) 659.10622(50) 663.24355(150) 667.36412(50) 671.46338(50) 675.54147(50) 679.59883(50) 683.63493(50)

v=4~3

HEDDERICH

ET AL.

1663

TABLE

1 (continued) Obs. - calc. /10-5 cm-1 4 6 6 11 13 9 11 6 6 3 0 12 -3 2 5 8 9 -2 -26 19 -1 19 -2 9 34 14 -20 3 34 13 41 -22 29 31 -20 -31 84 64 -2 271 -22 -I 35 3 -56 31 -3 -8 II 70 -3 4 -12 -12 19 13 -8 -24 3 6 12 6 -5 I

J" P48 P47 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P28 P27 P26 P25 P24 P23 P22 P21 P20 P19 P18 P17 P16 P15 PI4 P13 PI2 Pll PlO P9 P8 P7 P6 P5 P4 P3 P2 PI RO RI R2 R3 R4 R5 R6 R7 R8 R9 RIO RII R12 R13 RI5 RI6 RI7

Obs./cm-1 687.64923(50) 691.64100(50) 695.61031(50) 699.55677(50) 703.47971(50) 707.37895(50) 711.25435(50) 715.10502(50) 718.93082(50) 722.73143(50) 726.50642(50) 730.25548(50) 733.97812(50) 737.67426(50) 741.34315(50) 744.98473(50) 748.59889(50) 752.18426(50) 755.74152(50) 762.76918(50) 766.23995( 100) 769.67877(50) 773.08856(50) 776.46786(50) 779.81612(50) 783.13355(50) 786.41897(50) 789.67280(50) 792.89451(50) 796.08353(50) 799. 23978( 50) 802.36319(50) 805.45303(50) 808.50912(50) 811.53103(50) 814.51865(50) 817.47133(50) 820.38974(50) 823.27215(50) 826.11958(50) 828.93075(50) 831.70600(50) 834.44486(50) 837.14646(50) 839.81170(50) 842.43925(50) 845.02984(50) 850.09554(50) 852.57155(50) 855.00854(50) 857.40662(50) 859.76600(50) 862.08542(50) 864.36526(50) 866.60519(50) 868.80486(50) 870.96427(50) 873.08284(50) 875.16049(50) 877.19718(50) 879.19241(50) 883.05771(50) 884.92738(50) 886.75478(50)

Obs. - calc. /10-5 ern"! 8 -7 -9 1 -7 -11 12 10 7 8 7 8 1 13 4 5 40 7 10 8 110 0 6 14 4 29 4 4 9 -6 -18 -2 1 4 -5 -6 -35 7 -24 4 -8 3 19 -17 II 0 49 -19 7 -3 -14 24 9 5 4 -5 5 -2 -10 2 7 8 9 12

J" R18 R19 R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R30 R31 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R44 R45 R46 R47 R48 R49 R50 R52 R54 P57 P56 P55 P54 P53 P52 P51 P50 P49 P48 P47 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P34 P33 P32 P31 P30 P29 P28 P27 P26

Obs.Zcm"! 888.53957(50) 890.28173(50) 891.98095(50) 893.63709(50) 895.24986(50) 896.81903(50) 898.34452(50) 899.82602(50) 901.26345(50) 902.65654(50) 904.00516(50) 905.30926(50) 906.56825(50) 907.78243(50) 910.07504(50) 911.15319(50) 912.18567(50) 913.17222(50) 914.11269(50) 915.00775(50) 915.85593(50) 916.65813(50) 917.41343(50) 918.12241(50) 919.40004(50) 919.96811(50) 920.48895(50) 920.96316(50) 921.39014(50) 921.76922(50) 922.10129(50) 922.62144(50) 922.95179(50) 638.86621(50) 642.97601(50) 647.06761(50) 651.14147(100) 655.19459(50) 659.22747(50) 663.24355(300) 667.23339(50) 671.20542(50) 675.15624(50) 679.08464(50) 682.99066(100) 686.87564(50) 690.73652(50) 694.57445(50) 698.38898(50) 702.17991(100) 705.94515(50) 709.68645(50) 713.40242(50) 717.09308(50) 720.75821(50) 728.00889(50) 731.59387(50) 735.15166(50) 738.68227(50) 742.18469(50) 745.65885(50) 749.10425(50) 752.52062(50) 755.90785(50)

v=~4

1664

CAN. J. CHEM. VOL. 69, 1991

TABLE

1 (continued) Obs. - calc. /10-5 cm-1 16 45 9 -6 -12 -35 -27 7 0 -76 -39 85 30 71 -18 -35 -25 51 32 9 12 -27 -35 -29 1 7 14 -18 11 -3 51 -9 9 1 -8 -21 17 3 -10 -187 5 12 -7 2 24 -9 124 -8 -6 15 28 19 -342 26 87 -3 14 2 8 -30 -5 -23 1 -30

J" P24 P23 P22 P21 P20 P29 P18 P17 P16 P15 P14 P13 P12 Pll PIO P9 P8 P6 P5 P4 P3 P2 Rl R2 R3 R4 R5 R6 R7 R8 R9 Rl1 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R24 R25 R26 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44

Obs.Zcm"" 762.59288(50) 765.89020(50) 769.15714(50) 772 .39227 (50) 775.59618(50) 778.76916(50) 781. 90999(50) 785.01842(50) 788.09442(50) 791.13745(50) 794.14719(50) 797.12355(50) 800.06611(50) 802.97466(50) 805.84856(50) 808.68758(50) 811.49219(50) 816.99486(50) 819.69328(100) 822.35384(50) 824.98004(150) 827 .56823( 100) 837.54801(50) 839.94955(50) 842.31126(50) 844.63543(50) 846.92047(50) 849.16668(50) 851.37325(50) 853 .54035( 50) 855. 66776( 50) 859.80 190( 50) 861.80857(50) 863.77432(50) 865.69880(50) 867.58258(50) 869.42471(50) 871. 22522( 50) 872.98382(50) 874.70051(50) 876.37479(50) 878.00655(50) 879.59579(50) 882.64532(50) 884.10528(50) 885.52187(50) 886.89474(50) 888.22390(50) 889.50909(50) 890.75008(50) 891.94677(50) 893.09916(50) 894.20679(50) 895.26944(50) 896.28763(50) 897.26012(50) 898.18763(50) 899.07002(50) 899.90634(50) 900.69714(50) 901.44250(50) 902.14189(50) 902.79536(50) 903.40252(50)

Obs. - calc. /10-5 ern"! 1 12 5 4 -34 -3 6 2 11 11 2 4 6 18 5 -26 2 15 95 3 118 101 -17 58 -19 6 0 19 5 1 9 -5 14 15 -13 10 9 9 4 14 9 0 6 3 -1 2 -5 -3 -1 -4 -6 10 13 -2 31 3 1 25 -7 -26 -12 -5 11 9

J" R45 R46 R47 R48 R49 R50 R51 R55 P56 P54 P52 P51 P50 P49 P46 P45 P44 P43 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27 P26 P25 P23 P22 P20 P19 P18 P17 P16 P15 P13 P12 Pll PIO
P9

Obs.zcm"! 903.96352(50) 903.47840(50) 904.94617(50) 905.36761(50) 905.74250(50) 906.07049(50) 906.35198(50) 907.00830(50) 631.26624(50) 639.29894(100) 647.25691(50) 651.20753( 100) 655.13622(50) 659.04535(100) 670.64369(50) 674.46635(50) 678.26686(50) 682.04524(50) 685.79951(50) 689.53022(50) 693.23728(50) 696.91967(50) 700.57774(50) 704.21097(50) 707.81909(50) 711.40128(50) 714.95743(50) 718.48678(50) 721.99000(50) 725.46568(50) 728.91460(50) 732.33460(50) 735.72725(50) 739.09118(50) 742.42629(50) 745.73224(50) 752.25605(50) 755.47261(50) 761.81424(50) 764.93689(200) 768.03182(50) 771.09320(50) 774.12229(50) 777.11933(50) 783.01522(50) 785.91301(50) 788.77891(150) 791.60833(50) 794.40495(50) 797.16733(50) 799.89493(50) 802.58730(50) 805.24087(350) 807.86617(50) 813.00221(100) 825.19847(50) 827.52599(50) 829.81527(50) 832.06651 (50) 834.27886(50) 838.58819(50) 840.68389(50) 842.74058(50) 844.75707(50)

v=6~5

P8 P7 P6 P5 P4 P2 R2 R3 R4 R5 R6 R8 R9 RIO Rll

HEDDERICH TABLE

ET AL.

1665

1 (continued) Obs. - calc. /10-5 cm-1 -23 -12 -86 -7 -908 -47 -45 -82 7 -53 1 17 -23 -423 -63 -178 -76 -302 -6 -11 22 13 -71 -29 -69 -26 -56 -18 -3 -1 -22 -116 -51 29 1 -6 -136 188 396 . 17 5 -16 72 -14 -25 49 -11 173 16 -208 40 100 -32 -17 -37 -19 141 10 98 -3 31 -28 -11 -12

l"
R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R30 R3l R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R44 R45 R47 R50 R51 R54 P49 P48 P47 P46 P45 P44 P42 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P3l P30 P29 P28 P27 P26 P25 P24 P23 P22

Obs./cm-1 846.72833(600) 848.67116(50) 850.56750(50) 852.42330(50) 854.23959(50) 856.01250(50) 857.75264(700) 859.43674(50) 861.08708(50) 862.69487(50) 864.26104(50) 865.78496(50) 867.26622(50) 868.70521(50) 870.10125(50) 871.45421(50) 872.76452(50) 874.03130(50) 875.25442(50) 876.43369(50) 877 .56817(200) 878.66191(50) 879.70976(50) 880.71316(50) 881.67234(50) 882.58714(50) 883.45736(50) 884.28195(50) 885.06264(50) 885.79740(50) 886.48648( 150) 887.73275(100) 888.28561(50) 889. 25732( 100) 890.36885(50) 890.64793(50) 891.20663(50) 647.14517(100) 650.97177(50) 654.77918(200) 658.56125(50) 662.32515(100) 666.0651O( 100) 673.47846(50) 677.15168(100) 680.79849(150) 684.42469(50) 688.02566(50) 691.60208(100) 695.15490(50) 698.68078(50) 702.17991(200) 705.65682(50) 709.10513(50) 712.51815(1000) 715.92281(50) 719.29063(50) 722.63170(50) 725.94266(100) 729.23121(350) 732.48296(50) 735.70932(50) 738.90654(50) 742.07481(50)

Obs. - calc. /10-5 cm-1 -594 10 0 -9 10 -11 712 -27 18 -9 2 10 -9 3 -3 -22 6 10 -6 -44 -183 -1 2 -16 -17 -3 20 -40 4 -41 -136 85 -12 89 14 48 8 -58 -19 187 -20 116 54 12 88 -134 -38 -50 -66 45 -17 -197 -8 -52 -965 -19 -29 49 -89 362 -5 -17 -15 52

l"
P21 P20 P19 P18 P17 P16 P15 P14 P13 P12 Pll PIO P9 P8 P7 RO R3 R6 R7 R9 RIO R11 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27 R28 R29 R30 R3l R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R46 R49 P42 P38 P35 P33 P32 P30 P28 P27

Obs.Zcm"!
745.21175(50) 748.31931(50) 751.39546(100) 754.44228(50) 757.44812(1000) 760.44010(50) 763.39169(50) 766.31080(100) 769.19877(50) 772.05255(50) 774.87448(50) 777.66275(50) 780.41688(50) 783.13355(500) 785.82366(100) 806.05185(200) 813.04233(100) 819.69328(300) 821.83811(50) 826.00653(50) 828.03300(50) 830.02000(50) 831. 96699( 100) 833.87574(50) 835.74396(50) 837.57308(50) 839.36132(100) 841.10989(50) 842.81765(50) 844.48452(50) 846.11019(50) 847.69396(150) 849.23796(50) 850.74056(50) 852.20033(50) 853.61839(50) 854.99312(150) 856.33010(200) 857. 62348(400) 858.86836(50) 860.07412(50) 861.23685(50) 863.43413(100) 864.46643(50) 865.45592(50) 866.40256(50) 867.30403(50) 868.16397(200) 868.97640(50) 869.74394(250) 870.47184(50) 871.15340(100) 871.78846(50) 872.38031(50) 873.42902(50) 874.66493(50) 661.42085(150) 675.74003(50) 686.23006(100) 693.09693(50) 696.49270(50) 703.20429(50) 709.80945(50) 713.07091(50)

7--'>6

8--'>7

1666

CAN. 1. CHEM. TABLE

VOL. 69, 1991

1 (continued) Obs. - calc. /10-5 cm-1 26 8 27 17 11 8 14 22 29 18 47 42 178 26 58 19 7 14 32 16 13 23 20 29

J" P26 P25 P24 P23 P22 P2l P20 P19 P18 P17 P15 P14 R3 R4 R8 R9 RIO R13 R14 R15 R19 R25 R27 R28 R29 R30 R31 R32 R34 R37 R38 P49 P48 P47 P46 P45 P44 P43 P42 P41 P40 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27 P26 P25 P24 P23 P22 P2l P19 P18 P17 P16

Obs.Zcm"! 716.30457(50) 719.51041(50) 722.68777(50) 725.83593(50) 728.95561(50) 732.04517(50) 735.10512(50) 738.13524(50) 741.13479(50) 744.10391(50) 749.95028(150) 752.82567(150) 798.85770(150) 801.07990(150) 809.60458(1000) 811.62911(100) 813.62541(100) 819.37905(300) 821.22278(100) 823.02561(50) 829.83516(100) 838.83764(50) 841.50984(100) 842.78178(50) 844.01424(150) 845.20204(50) 846.34856(50) 847.45203(50) 849.53230(50) 852.33205(100) 853.17689(100) 751.39546(200) 756.18469(100) 760.94616(500) 765.68855(50) 770.39839(50) 775.08005(50) 779.73328(50) 784.35734(50) 788.95138(50) 793.51789(250) 802.55164(50) 807.02133(100) 811.46031(50) 815.86652(50) 820.23918(50) 824.57866(50) 828.88382(50) 833.15515(50) 837.39117(50) 841.59199(50) 845.75658(50) 849.88539(50) 853.97776(50) 858.03243(50) 862.04978(50) 866.02906(50) 869.96988(50) 873.87216(50) 881.55813(50) 885.34109(50) 889.08367(50) 892.78527(500

Obs. - calc, /10-5 cm-I -14 14 38 19 61 30 11 12 -10 -10 121 126 142 160 1080 81 79 -305 -59 29 -69 -28 91 -6 146 44 42 -21 -24 97 -64 174 -82 -442 13 -14 -37 -30 -19 -40 206 21 -68 -19 12 -8 5 -17 22 18 28 -6 5 40 16 17 8 -4 15 15 9 16 20

J" P15 P14 P13 P12 Pll

P9

Obs.Zcm"! 896.44556(50) 900.06386(50) 903.64038(50) 907.17407(50) 910.66485(50) 917.51612(50) 920.87587(50) 927.46149(50) 930.68665(50) 933.86603(50) 936.99984(50) 940.08696(50) 951 .96648(200) 954.81511(50) 957.61714(50) 960.36968(50) 963.07337(50) 968.33239(50) 970.88707(50) 973.39100(50) 975.84433(50) 978.24675(50) 980.59770(50) 982.89712(50) 985.14439(50) 987.33946(50) 989.48225(50) 991.57200(50) 993.60879(50) 995.59199(50) 997.52168(50) 999.39761(50) 1001.21912(50) 1002.98612(50) 1004.69906(50) 1006.35654(50) 1007.95899(50) 1009.50605(50) 1010.99719(50) 1012.43284(50) 1013.81195(50) 1015.13504(50) 1016.40130(50) 1017.61128(50) 1018.76427(50) 1019.85968(50) 1020.89828(50) 1021.87841(50) 1022.80178(50) 1023.66705(50) 1024.47393(50) 1025.22300(50) 1025.91354(50) 1026.54473(100) 1027.11936(100) 1027.63336(50) 1028.08907(50) 1028.48432(50) 1028.82102(100) 1029.09819(150) 1029.31757(50) 1029.47703(50) 1029.57530(50) 755.43538(100)

6LiF v = 1~0

v=2~1

P8 P6 P5 P4 P3 P2 Rl R2 R3 R4 R5 R7 R8 R9 RIO Rll R12 R13 R14 R15 R16 R17 R18 R19 R20 R2l R22 R23 R24 R25 R26 R27 R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R45 R46 R47 R48 R49 R50 R51 R52 P45

17
9 25 18 25 9 7 19 6 -15 27 15 18 24 2 19 -7 -3 -28 -7 11 -14 14 -52 -22 -13 -36

-17
-12 -88 50 9 36 -72 -113 -171 -62 11 -67 -67

HEDDERICH TABLE

ET AL.

1667

1 (continued) Obs. - calc. /1O~5 cm " -8 -9 -6 15 29 -5 -11 12 -1 -5 -30 -5 1 27 -16 -24 -23 -129 105 -47 -80 99 -22 14 -13 -33 -25 -52 -214 -252 -25 1 -31 50 289 2 -7 45 19 ·22 7 II 13 II 19 55 -15 19 -2 1 3 I 0 136 184 5 -24 14 -8 -5 -121 19 7 II

J" P43 P41 P40 P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27 P26 P25 P24 P23 P21 P20 PI9 PI8 P17 P16 P15 P14 P13 PI2 Pl1 P9 P8 P7 P6 P5 P4 P3 RI R2 R3 R4 R6 R7 R8 R9 RIO Rl1 R12 R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27

Obs./cm~l 764.61478(50) 773.67949(50) 778.16834(50) 782.62662(50) 787.05450(50) 791.45148(50) 795.81657(50) 800.14984(50) 804.45136(50) 808.71805(150) 812.95455(50) 817.15543(50) 821.32216(50) 825.45465(50) 829.55201(50) 833.61364(50) 837.63928(50) 841.62865(50) 845.58079(50) 849.49399(200) 857.21231(50) 861.01304(50) 864.77476(50) 868.49715(50) 872.17929(50) 875.82136(50) 879.42319(50) 882.98366(50) 886.50302(50) 889.98011(50) 893.41533(50) 900.15735(50) 903.46399(50) 906.72608(50) 909.94425(50) 913.11846(50) 916.24665(100) 919.33092(50) 934.05897(50) 936.86533(100) 939.62222(50) 942.33100(50) 947.60494(50) 950.16843(50) 952.68273(50) 955.14718(50) 957.56191 (50) 959.92643(50) 962.24050(50) 964.50353(50) 966.71581(50) 968.87667(50) 970.98505(50) 973.04232(50) 975.04697(50) 976.99921(50) 978.89871(50) 980.84527(50) 982.53819(50) 984.27761(50) 985.96322(50) 987.59499(50) 989.17244(50) 990.69572(50)

Obs. - calc. /1O~5 cm~l -45 -60 -10 -13 -6 9 -19 -37 8 -145 13 -15 -37 -16 3 3 4 20 0 -185 -5 5 13 28 -2 -17 6 -4 16 -9 0 -7 37 0 -18 17 -66 -18 -45 83 29 -36 -1 -2 7 -9 -6 -2 8 -3 21 44 -13 15 6 8 13 29 II -2 -14 -6 -2 39

J" R28 R29 R30 R31 R32 R33 R34 R35 R36 R37 R38 R39 R40 R41 R42 R43 R44 R45 R46 R47 R48 P41 P40 P38 P37 P36 P34 P33 P32 P31 P30 P29 P28 P27 P26 P25 P24 P22 P21 PI9 PI8 PI7 P16 PI5 PI4 P13 P12 Pll P9 P8 P7 P6 P5 P4 P2 R3 R4 R5 R7 R8 R9 RIO Rl1 RI2

Obs.z'cm"! 992.16338(50) 993.57652(50) 994.93450(50) 996.23725(50) 997.48431 (50) 998.67506(50) 999.81007(50) 1000.88915(50) 1001.91146(50) 1002.87728(50) 1003.78611 (50) 1004.63850(50) 1005.43360(50) 1006.17163(50) 1006.85155(50) 1007.47425(50) 1008.03932(50) 1008.54547(150) 1008.99703(150) 1009.38662(50) 1009.71917(50) 758.75890(100) 763.17149(50) 771.91079(50) 776.23471(50) 780.52789(50) 789.02044(50) 793.21835(50) 797.38225(250) 801.51430(250) 805.61544(50) 809.68058(50) 813.71070(50) 817.70707(50) 821.66970(300) 825.59133(50) 829.47955(50) 837.14646(50) 840.92343(50) 848.36390(50) 852.02613(50) 855.64945(50) 859.23324(50) 862.77709(50) 866.28072(50) 869.74394(50) 873.16500(50) 876.54562(50) 883.18000(50) 886.43358(50) 889.64414(50) 892.81130(50) 895.93473(50) 899.01544(150) 905.04087(200) 922.01884(50) 924.68524(50) 927.30477(50) 932.39898(50) 934.87365(50) 937. 29833( 150) 939.67647(50) 942.00368(50) 944.28135(50)

v= 3~2

1668

CAN. J. CHEM.VOL.

69, 1991

TABLE 1 (concluded) Obs. - calc. /10-5 ern"! -5 19 45 0 -6 -2 -26 14 -13 -24 -43 23 -4 -22 -39 Obs. - calc. /10-5 em-I -32 2 22 58 4 -19 22 -85 -34 9 -91 -63 -98 -23

J" R13 R14 R15 R16 R17 R18 R19 R20 R21 R22 R23 R24 R25 R26 R27

Obs.Zcm"! 946.50882(50) 948.68641(50) 950.81344(50) 952.88892(50) 954.91365(50) 956.88709(50) 958.80858(50) 960.67877(50) 962.49611 (50) 964.26116(50) 965.97345(50) 967.63365(50) 969.23974(50) 970.79251 (50) 972.29165(50)

J" R28 R29 R30 R31 R32 R33 R34 R35 R36 R38 R39 R40 R41 R43

Obs.zcm"! 973.73717(50) 975.12887(50) 976.46613(50) 977.74904(100) 978.97634(50) 980.14903(50) 981.26726(50) 982.32871(100) 983.33625(50) 985.18360(50) 986.02215(100) 986.80581 (50) 987 .53253( 100) 988.81787(50)

"Numbers in parentheses are estimated uncertainties. sities of the emission lines increased with higher temperature. The maximum temperature which is accessible with our current system is about 1500 K and it was at this temperature that the best emission spectrum was obtained. All emission signals decreased rapidly as the furnace cooled and disappeared at about 1200 K. TABLE2. Dunham constants for LiF (in em-I)" Value Constant YIO Y20 Y30 Y40 YOI YII Y21 Y31 Y41 Y02 Y12 Y22 Y32 Y03 Y13 Y23 7LiF 910.57272(10) -8.207956(46) 0.569166(82) -0.28437(49)E-3 I.34525715(57) -0.02028749(19) 0.156247(64)E-3 -0.3860(88)E-6 -0.870(45)E-8 -0.1174389(33)E-4 0.113878(9R)E-6 0.720(23)E-9 -0.306(13)E-1O 0.30449(55)E-1O 0.836(15)E-12 -0.270(27)E-13 6LiF 964.30621(22) -9.19819(12) 0.64808(20) 1.5087385(14) -0.02409773(41) 0.19766(15)E-0.736(21)E-6 -0.147719(13)E-4 0.15246(29)E-6 0.619(33)E-9 0.4300(35)E-1O 0.1120(70)E-II

III. Results The emission features were observed in the region where the infrared spectrum of MgFz was expected (Figs. 1,2). However, the high resolution spectrum showed a pattern typical of a diatomic molecule. After some thought and a literature search we found that the emission spectrum belonged to LiF (11). The presence of Li in our system was puzzling but in a previous experiment the alumina tube was used to vaporize LiNC. Despite careful cleaning of the cell, some Li remained on the walls of the alumina tube. At higher temperatures the MgF2 could react with water (which is always present in the system) and form HF. The HF can react with the Li impurities and produce LiF. Direct reduction of MgF2 with Li is also possible but MgF was not detected. An additional reaction of HF with the alumina tube took place to form AIF. The emission of AIF was observed in the spectrum (17). The spectral analysis program PC-DECOMP, developed by J. W. Brault, was used for data analysis. The rotational line profiles were fit to Voigt lineshape functions. The strong lines show a "ringing" caused by the (sin x/x) lineshape function of the Fourier transform spectrometer. The ringing was eliminated by using the "filter fitting" routine available in PCDECOMP. The signal-to-noise ratio for the strong lines was better than 1000 and the resulting resolution-enhanced line width was 0.0005 cm-I. The HF lines were used for absolute calibration (+/-0.0002 cm +) of the spectrum. For this calibration the HF absorption lines, taken in a spectrum at lower temperature, were calibrated against COz (18). The assignment of the vibrational bands of the main isotopomer 7LiF was straightforward (Table 1). Data reduction was made by using Dunham's equation (19)
[1] T(V,l)=L:Yij(v+~)i[J(J+l)]j
I,}

"Each isotopomer was fit independently. One standard deviation in parentheses.

were included in the fit. The Dunham coefficients obtained from this fit are shown in Table 2. The assignment of the vibrational bands of the minor isotop orner, 6LiF, was carried out by comparing predicted line positions with the unassigned lines in the spectrum. The line positions for 6LiF are also shown in Table 1. The mass-dependent Dunham coefficients Yij are listed in Table 2. Finally, all infrared and microwave data for LiF was combined and fit to the mass-reduced Dunham expression including Watson's correction due to the breakdown of the BornOppenheimer approximation (21,22)
[2] Yij = ~[(i+Zj)/ZlUij [1 +

(::J

~ij]

Pure rotational transitions reported by Pearson and Gordy (20)

where ~ is the reduced mass, Uij are the mass-independent parameters, mLi is the atomic mass ofLi (23), me is the electron mass, and ~ij is the mass scaling factor for the Li atom. The

HEDDERICH

ET AL.

1669

.S

6S0

720

760

SOO

Wavenumber

840

sso

no

1000

FIG. 1. Infrared spectrum of 7LiF.

1.0,-~--,-~~--,---~--,_...,-~~_~~~_~

.S

.2

.0 960 962

964

-------_j__~-

966

Wavenumber

968

970

972

974

FIG. 2. Infrared spectrum of 6LiF.

1670 TABLE3, Mass-reduced for LiF (in Constant Dunham constants

crn-I)a

CAN. 1. CHEM.VOL. 69, 1991 TABLE5. Rotational constants of ground state HFa Our work Constant Bo Do Ho Mo Jennings et al, (12) /crn-I 20.5597300(25) 2.1199I(14)E3 0.16334(50)E-6 -0.1473(66)E-1O 0.94(27)E-15

Our work 2061.15184(33) -42,05641(19) 0,660241(80) -7.480(lI)E-3 6,8926542(36) -0.2352993(16) 4.1016(14)E-3 -0.2259(44)E-4 -0.1199(52)E-5 -0.3083223(30)E-3 0.67650(42)E-5 0.991(25)E-7 -0.995(32)E-8 0.40964(30)E- 8 0.2566(34)E-9 -0.186(17)E-1O 0.0417(17) 0.3595(58)

/cm "
20.5597298(8) 2. I 19901(36)E-3 O. 163483(1 16)E-6 -0.14974(132)E-1O 0.1052(50)E-14

La

"Two standard deviations in parentheses.

data required two .'l's, one for VIO ("roe") and one for VOl ("Be"). The final mass-independent coefficients and the .'l's are listed in Table 3. The energy levels of HF were fit to the expression (24)
[3] Ev(J) = BvJ(J

I) - Dv[J(J

+
[J(J

l)f
+

+ Hv[J(J

1)]3

+ L;

1)]4

+ Mv[J(J

1)]5

aOne standard deviation in parentheses,

The fit includes all lines listed in Table 4 and Table 5 shows the determined constants. IV. Conclusion The high-resolution infrared emission spectra of LiF and HF were observed with a Fourier transform instrument. The ro-vibrational transitions of the fundamental band and of seven hot bands for 7UF and of three bands for 6LiF were rotationally analyzed. Pure rotational transitions for HF were also observed and enabled us to calculate an improved set of molecular constants. The accuracy of the line positions allows the use of HF as an absolute wavenumber standard. Acknowledgements The National Solar Observatory is operated by the Association of Universities for Research in Astronomy, Inc., under the contract with the National Science Foundation. We would like to thank J. W. Brault and J. Wagner for assistance in recording the spectra. This work was supported by the Astronautics Laboratory, Edwards Air Force Base, CA. Acknowledgement is made to the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this work. One of us (H.G.H.) thanks the Deutsche Forschungsgemeinschaft for a postdoctoral scholarship.
1. S. E. VEAZEYand W. GORDY. Phys. Rev. A, 138. 1303 (1965). 2. A. J. HEBERT,F. J. LOVAS,C. A. MELENDRES, . D. HOLLOWELL, C T. L. STORY, JR., and K. STREET, JR. J. Chern. Phys. 48. 2824 (1968). 3. G. L. VIDALE. J. Phys. Chern. 64, 314 (1960). 4. L. WHARTON,W. KLEMPERER,L. P. GOLD, R. STRAUCH,1. 1. GALLAGHER, nd V. E. DERR. J. Chern. Phys. 38, 1203 (1963). a 5. M. J. LINEVSKY.J. Chern. Phys. 34, 587 (1961). 6. M. J. LINEVSKY.J. Chern. Phys. 38, 658 (1963). 7. A. SNELSONand K. S. PITZER. J. Phys. Chern. 67. 882 (1963). 8. S. SCHLICKand O. SCHNEPP.J. Chern. Phys. 41, 463 (1964). 9. A. SNELSON.J. Chern. Phys. 46,3652 (1967). 10. S. ABRAMOWITZ, . ACQUISTA,and I. W. LEVIN. J. Res. Nat. N Bur. Stand. Sect. A, 72, 487 (1968). II. A. MAKI. J. Mol. Spectrosc. 102, 361 (1983). 12. D. A. JENNINGS, K. M. EVENSON, L. R. ZINK, C. DEMUYNCK, J. L. DESTOMBES,B. LEMOINE, and J. W. C. JOHNS. J. Mol. Spectrosc. 122. 477 (1987).

TABLE4. Pure rotational transitions of HF Obs. - calc. /10-5 em-I 0.181 0.139 -I 0 I 0 23 -14 9 -I II 4 8 38 -13 -15 -8 -8 -5 5 -3 74 62 -169 -II 0 Uncertainty (10')

J'
1 2 3 4 5 6 7 13 14 15 16 17 18 19 20 21 22 23 24 25 27 28 29 31 32 33

J"
0 1 2 3 4 5 6 12 13 14 15 16 17 18 19 20 21 22 23 24 26 27 28 30 31 32

Observed/ em-I
41.1109832a 82.1711179a 123. 12967a 163.93616a 204.54045b 244.89283b 284. 94444b 516.28061 c 552.92046C 588.89904c 624.17733c 658.71682c

/10-5

em-I

692.4812JC
725.43557c 757.54540c 788.78013c 819.10918c 848.50386c 876.93745c 904.38481 c 956.22816d 980.5832e l003.8672e

1047.15701067. 1377e
1085.98903
d

0.15 0.3 0.5 0.5 10 10 15 20 20 20 20 20 20 20 20 20 20 20 20 20 13 75 50 125 50 13

"Tunable far infrared spectroscopy (ref. 12). bFourier transform spectroscopy (ref. 12). "Fourier transform spectroscopy (our work). dDiode laser heterodyne spectroscopy (ref. 14). 'Diode laser spectroscopy (ref. 12).

HEDDERICH AL. ET 13. U. K. SENGUPTA,P. K. DAS, and K. N. RAo. J. Mol. Spectrosc. 74, 322 (1979). 14. D. A. JENNINGSand J. S. WELLS. J. Mol. Spectrosc. 130, 267 (1988). 15. J. S. WELLS, F. R. PETERSON,A. G. MAKI, and D. J. SUKLE. Appl. Opt. 20, 1676 (1981). 16. c. 1. FRUM, R. ENGLEMAN,JR., and P. F. BERNATH.J. Chern. Phys. 93, 5457 (1990). 17. H. G. HEDDERICH,C. 1. FRUM, R. ENGLEMAN,JR., and P. F. BERNATH.To be published. 18. G. GUELACHVILI K. N. RAo. Handbook of infrared standards. and Academic Press, Orlando, FL. 1986. 19. 20. 21. 22. 23.

1671

J. L. DUNHAM.Phys. Rev. 41, 721 (1932). E. F. PEARSONand W. GoRDY. Phys. Rev. 177, 52 (1969). J. K. G. WATSON.J. Mol. Spectrosc. 45, 99 (1973). J. K. G. WATSON.J. Mol. Spectrosc. 80, 411 (1980). H. S. PEISER, N. E. HOLDEN, P. DE BIEVRE, 1. L. BARNES, R. HAGEMANN, . R. DELAETER,T. J. MURPHY,E. ROTH,M. SHIMA, J and H. G. THODE. Pure Appl. Chern. 56, 695 (1984). 24. W. GORDY and R. L. COOK. Microwave molecular spectra. Wiley, New York, NY. 1984.