R.S. Ram and P.F. Bernath- Fourier Transform Spectroscopy of the A^2-Pi-i-X^2-Sigma^+ System of CP

8/2/2019 R.S. Ram and P.F. Bernath- Fourier Transform Spectroscopy of the A^2-Pi-i-X^2-Sigma^+ System of CP

1/11


2/11

,@IIi-XZ~+ TRANSITION OF CP 283

_..I. ~ 1.-. .~-~~- - -. 1cm-7 6805 6610 6815 -- 6620

FIG. 1. Part of the rotational structure of the O-O band of the AZI13,#Z+ transition near the +B and+3B bandheads.

agrees with the original work of He&erg (I), who attributed the presence of carbonin his discharge to tap grease and sealing wax.The emission from the discharge was observed with the Fourier transform spec-trometer associated with the National Solar Observatory at Kitt Peak. Nine scanswere coadded in 1 hr of integration. The unapodized resolution was set to 0.02 cm-.InSb detectors and a silicon filter restricted the spectrum to the 1800- to 8800-cm-region.The molecules CO, PH, HZ, Cz, and P2 were observed as well as emission fromvarious atoms. The analysis of the vibration-rotation spectrum of PH is being publishedseparately (12). The CO (I-?) and PH (14) lines were used to provide the absolutecalibration of our spectra.

RESULTS AND DISCUSSIONThe interferograms were transformed by standard methods to provide the spectrum.Some ringing was present, particularly near strong atomic lines, so the spectrum wasslightly apodized. The final linewidth of the CP emission features was about 0.040cm- (FWHM).The line positions were extracted with the aid of a data reduction program calledDECOMP developed at Kitt Peak. To find the peak positions, a Voigt lineshape func-tion was fitted to the CP lines by a nonlinear least-squares procedure.Five vibrational bands of the A211-X22+ transition were observed: l-0, O-O, O-l,O-2, and 3-l (see Fig. 1). For the 3-1 band only the 211j/2-22+ subband was found

because the Si filter prevented the observation ofthe corresponding 2111,2-2Z+ ubband.The other bands either had poor Franck-Condon factors (e.g., 2-1) or were obscuredby strong P2 emission (e.g., 2-2). The National Solar Observatory is operated by the Association of Universities for Research in Astronomy,Inc., under contract with the National Science Foundation.


3/11


4/11

4r.5 6819.2921~-2)

A211i-XzZ+ TRANSITION OF CPTABLE I-Continued

AqlJ,2 - x5+ 0-OPl Ql R12

6782.5960,1,13.5 6819.0642,-l,14.5 6818.6554,-9,15.5 681Q.O676,-6,16.5 ffl17.3005,-2,17.5 6616.3534,4)16.5 6815.2269,,4,19.5 6813.9178(-3,20.5 6812.4307,-2,21.5 6910.7634,-4,22.5 66808.917718,23.5 6+X,6873,-29)24.5 6w4.6841,4,25.5 6602.2973~-2,26.5 6799.7301,-14,27.5 67%.9853(-6,28.5 6794.0%9,-17,29.5 6790.95521-5,30.5 6767.6701(-,I,31.5 6784.2066(-6,32.5 6780.5639C3,33.5 6776.7400(-7,34.5 6772.7361,-Z,35.5 6766.5559,-7,36.5 6764.1947,~8,37.5 6739.6547,-6,36.5 6754.9352,-6,39.5 6750.034#-29,40.5 6744.V609~14,41.5 67399.7057,29,42.5 6734;2711U?,43.5 6726.6521(-6144.5 6722.8476(-117,45.5 67,6.886OW,46.5 6710.7372,7,

6779.5487(O)6776.3219(-5)6772.9169,-2)6769.3330< 3,6765.5693(O)676,.6274(-O6757.5074,8,6753.20+35(-6,6746.7287,-2,6744.0721(-1,6739.2366,-4,6734.223712,6729.0309,-7,672X6616,1,671.9.1129,-4,6712.3664,-716706.4834~516700.40+4(-5,66%.1410(-1,6687.7046~9,6681.0887,-l,6674.2984,20,6667.3278f 10,6660.1792,-7,6652.8552,~616645.3570,20,6637.67644(-6,6629.8231~4,6613.5794(-4516605.19981-1,6596.6423,2?,6567.WlS,-16,

6800.2405,-l,67?8.6031,-4,6796.7670, I,67?4.7?07~-3,6792.6164~7,67VO.2566,-25,6787.7269(-3,6785.01366(-4,6782.1213,-4,6779.050210,6775.7993(-3)6772.3700~0,6768.76!1(-3,6764.?738~-1,6761.0073,-216756.8621,-2,6752.538310,6746.0361,4,6743.3545(0,6736.4946,-2,6733.4564(-216728.2397(-4)6722.8476124,6717.2716!-6,67, ,.5206,-4,6705.5907,-10)6699.4.947(2,66?3.1974,-21,66&X7346,-20,6660.09%,5,6673.2780(O)66&X.2607(-17,6639.1098~4,6651.7571,-20,

6798.8533,-5,6797.0550(-616795.0760(-4)6792.?209~-6)6790.5650,-6)6788.06?6,-6,6765.375!(-5,6782.503OC 12,6779.4467(-2,6776.2189,20,6772.8063(3>6769.2(59


5/11

286 RAM AND BERNATHTABLE I-Continued

&,,2 - x3+ 1-oR2 p2 Q2 R21 p21 021

26.5 7965.9003~3,27.5 796!.620?,6~28.5 7957.,601(-5,29.5 7952.520x-22,30.5 7947.7061~15,31.5 7942.7085,6)32.5 7937.5326~7~33.5 7932.1755(-12,34.5 7926.6404(-18135.5 7Prn.9322~39,36.5 7915.0364(13,37.5 7906.95682~-43)38.5 7902.7111~7,39.5 78%.2772(-l?,.0.5 ?%P.6669


6/11

A*&X22+ TRANSITION OF CP

TABLE I-Continued

287

r?n,,* x*2+ o-1R2 p2 Q2 R21 P2I 921

1.5 5738.4164,-2,)2.5 5736.6633,14)5.5 5738.7906,21~1.5 57%.7357,-45,5.5 5736.5562,-2,6.5 5736.1766,7,7.5 5737.6654,1216.5 5736.9944(-10)9.5 5736.1672,~43,

10.5 5735.1699(-26)11.5 5734.05433~ I)12.5 5732.7663,~4113.5 5731.3243,Jl14.5 5729.7260~20,15.5 5727.9693(5)16.5 5726.0581~-1)17.5 5723.9916~4,16.5 5121.7715~7,19.5 5719.3944,4,20.5 5716.661X-1121.5 5,14.1,45(5)22.5 5711.3357~49~23.5 5706.3319(-1)21.5 5705.1774,-2)25.5 5701.6717~42~26.5 5698.4011~-8,27.5 5694.7601,~4)28.5 5691.0027,-7)29.5 5687.0716~ 10,50.5 5682.977X-4,)31.5 56,6.,3%7~!1,52.5 5674.3374(1,53.5 5669.7623( 12)34.5 5665.0681(-9)35.5 5660,200,~-3)36.5 5655.,756(-14)37.5 5649.9966(-2,36.5 5644.6603(-6139.5 5639.1706~20~40.5 563,.5169(-1,)41.5 5627.71.X-17,42.5 5621.7541~-16)43.5 5615.6361(-9,44.5 5609.3656(-3,45.5 5602.933lC-39)

5730.1220(-17)5727.3771(-36)5724.465x*4>5721.4214-9,~5716.2269,27)5714.6640,Iro5711.3378~-6715707.6756,-l,5703.6508, I,5699.6716(715695.7374,315691.4482,~4)5687.0051,-615682.4034-54,5677.6580,6)567*.7517(-l,5667.69*1,2)5662.4780,1)565,.1,035651.5869(-6,5645.9107~4~5640.0813,6,5634.0927,-36356*,.9565(-M,5621.666904)56!5.2lW-8)5608.6160~-10)5601.6626(-2115594.9568(-21

5560.68130,~5573.3106(Z)5%5.7860~-17)5556.1 lO3(-8,5550.2616(6>5542.2966~-1)5534154X-52)55*5.8660(-25,5517.426425,5506.6282,*3,5500.0739(-635491.1728~,2,54682.1059(-5535472.9024~26~

5734.63*5,-263573,.6596(-,035732.3353(, >5,30.8529(-1)57*9.2167(8,5727,4*23~-1735725.4714(-6015,2,.,762(3)57*1.1*05~6~5716.7093~6~5716.143X4,5713.4228,4)5710.5477(6)5707.5174~3~5704.3327,3,5700.9977,4,,5697.4991(3)569,.850*(2,5690.043X-3115666.0691~10~5661.9754(,)56,,.7079(4,56,3.285*~,~5666.7063~2~5663.9,4&- I5,5659.0681(-16)5654.046X-3,5646.85,3(,)5643.5026~*~5637.99,5( 115632.3397(* I,5626.5214(-16156*0.5547,7)5614.4300(-215606.,5155747.6377(-4,5749.031 l(2)5750.0686(3,5,50.95!5~8~5751.6774(-215752.2.l90(-1)5752.6657(,,5752.9253(-115753.0309(6)5752.9791,-J)5752.,,26(-3,5752.4106~0~5751.8923(-1)5751.2,67(3)5,50.,877(-7)5X9.4029(5)5746.2562(-2215746.96*4(2)

5743.6969(-315742. ,*94(-8)5740.2071~2~5736.1276~6~5,35.8812~-97,5733.4976(-5)5730.9552~65~5726.2413~-13)5725.381609)5722.361202)5,,9.,827(-6,5715.851000~57,2.3566~-7)5706.7114-6,5704.9071(-3,5700.9411~45~5696.8256(-6,5692.5510(6)5688.1171~5~5683.5253(-Z)

5733.601 l(33)5,32.20995669.6603(-6815765.691604,5661.5582(-7,5677.2733~6,56,2.6,2,~4,5668.*3,5(-3)5663.4863(*35658.5612~0~5653.5204(-12)5646.3047(-26)5642.9392,9)56,7.4 145(-2,5631.,360


7/11

RAM AND BERNATH

TABLE I-Continued

P l

1 5 . 5 5 59 3 . 3 7 8 1 ( - 2 ,1 6 . 5 5 5 9 2 . 6 0 1 2 ( - 1 0 ,1 7 . 5 5 59 2 . 0 5 7 3 ( - 9 )1 6 . 5 5 5 9 1 . 1 4 7 4 ~ 1 1 ~1 9 . 5 5 59 0 . 0 6 6 2 ( - 3 12 0 . 5 5 %8 . 6 1 6 2 ~ - 6 ,2 1 . 5 5 5 8 7 . 4 0 2 6 ( - 7 12 2 . 5 5 5 6 5 . 8 1 8 6 ( - 1 3 ,2 3 . 5 5 5 6 4 . 0 6 6 9 ( - 1 9 12 4 . 5 5 5 6 2 . , 4 6 9 ~ - 1 0 12 5 . 5 5 %0 . 0 6 3 4 ( 2 ,2 6 . 5 5 5 7 , . 6 0 8 4 ( - 4 12 7 . 5 5 5 7 5 . 3 8 4 2 ( - 2 5 )2 6 . 5 5 5 , 2 . , 9 6 7 , - Z ,2 9 . 5 5 5 7 0 . 0 3 9 4 ( - 2 )3 0 . 5 5 5 6 7 . 1 1 4 7 , , )3 1 . 5 %6 4 . 0 2 3 9 ( 1 7 ,3 2 . 5 5 5 6 0 . 7 6 2 Ot - 3 ,3 3 . 5 5 5 5 , . 3 , 2 2 ( - 2 7 ,3 4 . 5 5 5 5 3 . 7 4 , 0 ( 9 ,3 5 . 5 -3 6 . 5 5 5 4 6 . 0 4 7 5 ( - 1 2 13 1 . 5 5 5 4 1 . 9 3 4 7 ( 2 6 ,3 8 . 5 5 5 3 7 . 6 6 6 2 ( - Z ,3 9 . 5 5 5 3 3 . 2 5 7 2 ( - 4 ,4 0 . 5 5 5 2 6 . 6 6 3 6 6 ( 3 9 ,4 1 . 5 -4 2 . 5 5 5 1 8 . 9 6 3 3 ~ 2 ,4 3 . 5 5 5 , 3 . 8 6 %6 ( 1 1 ,4 4 . 5 5 5 0 6 . 5 9 6 7 ( - 4 14 5 . 5 5 5 0 3 . 1 5 3 7 ( - 1 3 4 1

5 5 4 6 . 2 2 6 9 ( 2 0 ,5 5 4 4 . 8 5 8 , , 3 6 ,5 5 4 1 . 2 7 4 7 ( O )5 5 3 7 . 5 4 6 2 ( O )5 5 3 3 . 6 5 5 3 ( 3 ,5 5 2 9 . 4 9 4 7 ( - 3 ,5 5 2 5 . 3 6 X+ ( , ,5 5 2 0 . 9 7 5 0 ( - J ,5 5 1 6 . 4 1 5 1 ( - 5 ,5 5 1 1 . 6 6 9 1 ( - 5 )5 5 @3 . 7 9 7 7 ( 4 ,5 5 0 1 . 7 3 9 7 ( 9 ,5 4 9 6 . 5 1 4 2 ( 1 ,5 4 9 1 . 1 2 6 2 ( 2 6 ,5 4 8 5 . 5 6 6 X- 3 ,5 4 7 9 . 8 4 %( - 1 3 ,5 4 1 3 . 9 4 9 6 ( - 6 6 ,5 4 6 7 . 9 1 5 8 ( 1 3 5 ,5 4 6 1 . 6 6 8 7 ~ 5 7 ,5 4 5 5 . 2 9 3 3 ( - 5 0 ,5 4 4 6 . 7 4 6 5 ( 2 ,5 4 4 2 . 0 3 6 2 ~ 3 1 35 4 3 5 . 1 5 1 0 ( - 1 6 ,3 4 2 6 . 1 , 1 4 ~ 3 6 ~Y2 0 . 8 9 7 6 ( 2 ,5 4 1 3 . 5 2 3 1 ( 2 ,5 4 0 5 . 9 8 2 6 ( - 1 0 ,5 3 9 6 . 2 , 4 3 ( - 5 5 ,5 3 9 0 . 4 1 2 7 ( , 0 )

5 3 7 4 . 1 6 4 X1 2 ,

5 5 7 0 . 1 0 0 6 , - 1 ,5 5 6 8 . ! 1 7 0 ( - 2 ,5 5 6 5 . 9 6 6 0 ( - 2 ,5 5 6 3 . 6 4 6 2 ( - 1 7 ,5 5 6 1 . 1 6 2 5 ( 1 ,5 5 5 8 . 5 0 9 2 < - 4 ,5 5 5 5 . 6 8 8 9 ( - 6 ,5 5 5 2 . 7 0 3 2 ( 5 )5 5 4 9 . 5 4 6 # - 3 )5 5 4 6 . 2 2 , , ( - 5 ,5 5 4 2 . 7 3 9 , ( - 5 ,5 5 3 9 . 0 8 3 0 ( - 1 7 ,5 5 3 5 . 2 6 3 2 ( 1 ,5 5 3 1 . 2 7 4 9 ~ 2 ,5 5 2 7 . , , 9 2 ( - 4 ,5 5 2 2 . 7 9 7 6 ( - 4 ,5 5 1 8 . 3 1 3 7 ( 3 9 ,5 5 1 3 . 6 5 4 X- 6 ,5 5 0 6 . 6 3 2 6 ( - 1 7 ,5 %3 . 8 4 7 2 ( t )5 4 9 6 . 6 9 2 X- 1 0 ,5 4 9 3 . 3 7 2 8 ( - 1 3 ,5 4 6 7 . 6 8 8 9 ~ 5 ~5 4 6 2 . 2 %8 ( - 4 ,5 4 7 6 . 4 1 6 6 ( - 3 3 ,5 4 , 0 . 4 3 , 4 ( 6 ,5 4 6 4 . 2 6 6 X2 ,5 4 5 , . 9 , 4 2 ( J )5 4 5 1 . 4 9 7 4 ( 3 2 ,5 4 4 4 . 8 5 1 2 ( 2 0 ,5 4 3 &0 3 7 6 , - 1 4 ,

5 5 6 6 . 4 2 3 0 ( 5 ,5 5 6 6 . 2 9 0 4 ( 4 )5 5 6 3 . 9 9 1 2 ( 1 0 ~5 %1 . 5 2 3 7 ( 6 ,5 5 %. 8 9 0 6 ( 1 7 ,5 5 3 6 . 0 6 7 5 l 0 ,5 5 5 3 . 1 2 %0 ( 4 1 )

5 5 4 6 . 6 8 0 4 ~ - 4 ,5 5 4 3 . 2 1 0 4 ~ - 1 0 15 5 3 9 . 5 7 3 9 ( - 1 1 ,5 5 3 5 . 7 7 , 2 , - 6 15 5 3 1 . 6 0 0 4 ( - 1 6 ,5 5 2 7 . 6 6 4 1 ( - 1 3 ,5 5 2 3 . 3 6 1 7 ( - 6 ,5 5 1 . X6 9 2 6 ( 0 ,5 5 1 4 . 2 3 5 8 ~ - 7 ,5 3 0 9 . 4 5 2 8 ~ - 1 3 ,5 5 0 4 . 4 6 6 9 ( 1 6 ,5 4 9 9 . 3 5 1 4 l l 0 ,5 4 9 4 . 0 6 2 6 ( 1 3 2 ,5 4 6 6 . 5 8 5 , ( 3 3 ,5 4 8 2 . 9 4 8 9 ( - 5 ,5 4 7 7 . , 4 9 3 ( - 1 3 ,5 4 , 1 . 1 6 %( - 3 ,5 4 6 5 . 0 5 4 3 , - 1 6 )5 4 5 8 . , 6 1 5 ( , 3 ,5 4 5 2 . 2 9 8 X- 3 ,

5 5 2 3 . 2 7 0 4 ~ 2 ,5 5 1 6 . 3 1 3 7 ( - 7 3 ,5 5 1 3 . 2 0 5 %0 ,5 5 0 7 . 9 2 3 7 ( - 1 15 5 0 2 . 4 , 6 3 ( 4 ,5 4 9 6 . 6 6 6 6 ( 4 , ,5 4 9 1 . 0 6 1 9 ( - 5 ,5 4 6 5 . 1 3 1 9 ( - 4 9 ,5 4 7 9 . 0 2 5 5 ( - l ,5 4 , 2 . , 4 9 , ( 8 >5 4 6 6 . 3 0 5 1 ( - 1 6 1

5 4 5 2 . 9 2 7 9 ( , 3 ,5 4 4 5 . 9 6 4 7 ( - 4 2 ,5 4 x ) . 6 8 5 0 ( - 1 4 ,5 4 , 1 . 6 2 1 4 , 2 4 ,5 4 2 4 . 1 6 6 , , - 3 ,5 4 , 6 . 5 9 0 7 , 3 ,5 4 0 6 . 8 3 0 0 ( 5 ,5 4 0 0 . 9 0 7 2 ~ 2 7 ,5 3 9 2 . 8 1 4 6 ( - 7 ,

5 3 7 6 . 1 5 2 0 ~ 6 7 ,5 3 6 7 . 5 6 3 9 ( - 1 0 35 3 5 &6 2 2 6 ~ l , ,5 3 4 9 . 9 1 7 1 u 5 ,5 3 4 0 . 8 4 4 6 ( 1 4 ,

5 5 4 5 . 1 , 9 4 , - 1 ,5 5 4 1 . 5 9 6 1 ( - J ,5 5 3 7 . 8 9 0 3 ( - Z ,5 5 3 4 . 0 1 5 3 ( - 4 ,5 5 2 9 . 9 7 5 9 ( , 6 ,5 5 2 5 . 7 6 %6 ( - 6 ,5 5 2 1 . 3 9 , 1 ~ - 4 )5 5 1 6 . 6 4 9 9 , - 5 )5 5 1 2 . 1 4 2 5 ( - 4 ,5 5 0 7 . 2 6 6 0 ( - 1 1 ,5 5 0 2 . 2 3 0 %1 5 ,5 4 9 7 . 0 2 2 4 ( - 5 ,5 4 9 1 . 6 5 1 3 ( 6 ,5 4 6 6 . , , , 5 ( - 1 1 15 4 6 0 . 4 0 9 4 ~ 8 ,5 4 7 4 . 5 3 6 2 ( - 7 ,5 4 6 8 . 5 0 2 6 ( - 1 0 ,5 4 6 2 . 3 0 3 3 ( 5 ,5 4 5 5 . 9 %9 ( 3 ,5 4 4 9 . 4 0 5 0 ( - 1 ,5 4 4 2 . 7 0 6 4 ( - 2 0 ,5 4 3 5 . 6 4 6 0 ( - 6 ,5 4 2 6 . 8 1 9 6 ( - 3 ,5 4 2 1 . 6 2 6 2 , - 2 ,5 4 1 4 . 2 7 0 5 , - l , ,5 4 0 6 . 7 5 1 6 ( 3 )5 3 9 9 . 0 6 9 8 ( 3 , ,5 3 9 1 . 2 1 6 1 ( 1 6 ,5 3 a 3 . 1 9 9 4 , - 3 4 ,5 3 7 5 . 0 2 6 W1 4 ,5 3 6 6 . 6 8 3 4 ( Z )

k n l , 2 - x 2 z + o - 2

0 . 51 . 52 . 53 . 54 . 5 4 5 2 6 . 4 7 0 9 ( - 1 9 ,5 . 5 4 5 2 6 . 3 5 4 4 ( l 3 1 ,6 . 5 4 5 2 6 . 0 6 7 9 ( 1 2 ,7 . 5 4 5 2 5 . 6 4 9 4 ( 4 ,6 . 3 4 5 2 5 . 0 6 6 9 ( 6 ,9 . 5 4 5 2 4 . 3 6 2 6 ( - 1 6 ,

1 0 . 5 4 5 2 3 . 5 %, ( - 7 ,1 1 . 5 4 5 2 2 . 5 4 6 5 ( ! 3 ,1 2 . 5 4 5 2 1 . 4 1 2 5 ( - 1 2 ,1 3 . 5 4 5 2 0 . 1 3 6 0 ( - I I ,1 4 . 5 4 5 1 8 . 7 1 7 2 ~ 0 ,1 5 . 5 4 5 1 7 . 1 5 4 4 ( 4 )l b 5 4 5 1 5 . 4 4 5 9 ( - ( 6 ,1 7 . 5 4 5 1 3 . 5 9 6 0 ~ 3 ,1 6 . 5 4 5 1 1 . 6 0 4 6 ( 1 ,1 9 . 5 4 5 0 9 . 4 6 9 0 ( 1 1 ,2 0 . 5 4 5 0 7 . 1 8 9 6 ( 1 7 ,2 1 . 5 4 5 0 4 . X 4 0( - 4 ,2 2 . 5 4 5 0 2 . 1 9 7 3 ( - l ,2 3 . 5 4 4 9 9 . 4 6 2 3 ( - 4 6 ,2 4 . 5 4 4 9 6 . 6 3 3 2 ( 3 ,2 5 . 5 4 4 9 3 . 6 3 5 5 ( 3 ,2 6 . 5 4 4 9 0 . 4 9 0 6 ( - 3 4 12 7 . 5 4 4 6 , . 2 , 0 9 ~ 1 , ,2 6 . 5 4 4 6 3 . 7 8 0 1 , - 6 ,2 9 . 5 4 4 6 0 . 2 0 8 Hl ,

4 5 1 7 . , 4 6 1 , - 2 5 ,4 5 1 5 . 0 5 4 7 , 9 ,4 5 1 2 . 2 1 2 6 ~ - 3 6 ,4 5 0 9 . 2 3 4 6 ( - 1 3 ,4 5 0 6 . 1 1 3 6 ( 6 ,4 H) 2 . 8 4 , , , 2 ,4 4 9 9 . 4 %1 ( - 1 3 ,4 4 9 5 . 8 6 6 5 ( - S ,4 4 9 2 . 1 9 3 6 ~ - 1 6 ,4 4 6 6 . 3 3 6 6 ( - 1 3 ,4 4 6 4 . 3 6 2 1 ~ 0 ,4 4 6 0 . 2 6 2 4 ( 7 ,4 4 7 6 . 0 0 0 5 ( , 5 ,4 4 7 , . 5 9 2 3 , - 1 5 ,4 4 6 7 . 0 4 6 6 ( O )4 4 6 2 . 3 5 6 2 ( - 1 1 ,4 4 5 7 . 5 2 6 2 ( 6 ,4 4 5 2 . 3 5 1 4 ( - 4 ,4 4 4 7 . 4 %X7 ,4 4 4 2 . 1 , 7 1 ( - 7 ,4 4 %. 7 , 9 6 ( , 9 ,4 4 3 1 . 2 3 %( - l ,4 4 2 5 . 5 5 0 4 ( - 1 2 ,4 4 1 9 . 7 2 6 2 1 6 ,4 4 1 3 . 7 5 7 6 ~ 2 ,4 4 0 7 . 6 4 6 6 ( , 0 ,4 4 0 1 . 3 9 %( - 6 ,

4 5 2 0 . 0 0 9 2 ~ 1 2 ,4 5 1 8 . 5 6 4 3 ~ - 1 5 ,4 5 , 7 . 0 1 7 7 ( - 3 1 ,

4 5 , 3 . 4 6 0 9 ( - 1 3 ,4 5 1 1 . 4 7 l 7 l 2 9 ,4 5 0 9 . 3 3 2 0 ( - 6 ,4 5 0 7 . 0 5 2 9 l - 7 ,4 5 0 4 . 6 3 1 5 ( - 4 )4 5 0 2 . 0 6 6 6 ( - 6 ,4 4 9 9 . 3 5 9 6 ( - 6 ,4 4 9 6 . 5 1 0 2 ( - l ,4 4 9 , . 5 1 6 X- 1 0 ,4 4 9 0 . 3 6 1 6 ( - 6 ,4 4 8 7 . 1 0 4 6 ~ 5 ,4 4 6 3 . 6 8 2 5 ( - ( 2 14 4 6 0 . , , 9 8 ~- 5 ,4 4 , 6 , 4 , 4 0 ( - Z ,4 4 X5 6 5 3 ( - 2 ,4 4 6 8 . 5 7 5 %1 4 ,4 4 6 4 . 4 4 %( , 7 )4 4 6 0 . 1 6 6 X3 3 ,4 4 5 5 . 7 4 6 X2 7 ,4 4 5 1 . 1 6 1 2 ~ - 9 ,

4 4 4 1 . 6 2 7 4 , - 2 9 ,4 4 3 6 . 6 4 0 9 , 5 ,

4 3 2 7 . , 0 2 , ~ 3 1 ,4 5 2 9 . 0 6 2 6 ~ 2 6 ~4 5 3 0 . 9 1 6 2 ( - 1 3 34 5 3 2 . 6 0 9 3 ( - 2 6 ,4 5 3 4 . 1 6 3 3 ~ 2 ,4 5 3 5 . 5 6 9 6 , - 1 6 ,4 5 3 6 . 6 X4 ( - 2 7 ,4 5 3 7 . 9 5 7 2 ( - S ,4 5 3 6 . 9 3 9 9 H3 3 ,4 5 3 9 . , 6 9 1 ( - 1 6 )4 5 4 0 . 4 6 3 0 , 6 ,4 5 4 1 . 0 1 1 0 ~ 5 ,4 5 4 1 . 4 1 3 6 ( 6 ,4 X, . 6 , %, - 3 ,4 5 4 1 . , 6 6 9 , - 4 3 ,4 5 4 1 . , 6 6 , , 2 0 ,4 5 4 , . 5 9 7 3 , 7 ,4 5 4 1 . 2 6 2 0 , - 6 ,4 5 4 0 . 8 2 5 3 ( 6 ,4 5 4 0 . 2 2 2 4 , - 6 ,4 5 3 9 . 4 8 1 5 ( 4 3 ,4 5 %. 5 6 6 6 ( - 8 )4 5 3 7 . 5 5 5 0 ( 1 5 ,4 5 %. 3 7 4 6 , - 7 ,4 5 , 5 . 0 5 0 5 , - Z , ,4 5 3 3 . 5 6 6 9 ~ 2 ~4 5 3 1 . 9 , 6 3 , 5 ,4 5 3 0 . 2 1 6 6 , - 4 0 ,4 5 2 6 . 3 2 0 6 ~ - 04 5 2 6 . 2 7 6 6 ~ 1 ,

4 5 1 9 . 9 2 1 7 ( - 3 3 )

4 5 0 1 . 8 2 0 0 ( 1 7 ,

4 5 1 8 . 4 6 5 4 ~ , 1 ,4 5 1 6 . 9 0 0 4 ( - 4 1

4 4 9 9 . 0 ? 2 9 ( 3 ,

4 5 1 5 . 1 7 3 9 9 ( - 6 ,4 5 1 3 . x 6 1 ( 7 ,4 5 1 1 . 2 9 4 O( S ,4 5 0 9 . 1 3 6 9 ( ! ,4 5 0 6 . 8 4 , 7 ( 3 )4 5 W 3 9 8 6 ~- 2 6 ~

4493.2155~23,4 4 9 0 . 0 6 , , , , 7 ,

4 4 9 6 . 2 2 6 0 ( , 7 ,

4 4 7 9 . 7 4 3 0 ( , 1 ,4 4 , 6 . 0 1 3 2 ( - 4 2 ,

4 4 6 8 . 1 4 1 1 ~ 7 ,4 4 6 5 . 9 6 7 9 ( O )4 4 5 9 . 6 9 6 6 ( 4 0 ,4 4 5 5 . 2 5 6 2 ( 1 2 ,4 4 5 0 . 6 , 4 2 ( - 4 ,4 4 4 5 . 9 5 5 1 ( 3 6 ,4 4 4 1 . 0 9 0 6 ~ 5 0 ,

4 5 2 6 . 5 6 9 9 ( - 1 4 ,4 5 2 6 . 2 2 2 5 ( 1 2 ~

4 5 2 1 . 1 6 4 6 ( 0 ,

4 5 2 5 . 9 3 2 7 ( 4 4 ,4 5 2 5 . 4 9 3 4 ( 1 2 3

4 5 1 9 . 8 6 9 X2 ,

4 5 2 4 . 9 0 9 0 ( - 4 0 ,4 5 2 4 . , 6 9 5 ( - 1 , )4 5 2 3 . 3 2 6 7 ( 1 6 ,4 5 2 2 . 3 1 5 8 ( - 7 ,

4 5 1 3 . 2 5 8 6 ( 2 S ,

4 5 1 6 . 8 5 1 5 ~ 2 0 ,

4 5 l , . 2 4 , 7 Ul ,4 5 m. 0 9 4 1 ~ 4 5 3

4 5 1 5 . 1 2 3 2 ( - 1 4 ,

4 5 0 6 . 7 9 4 4 ( 3 3 ,4 5 0 4 . 3 4 7 1 ( - 2 0 ,4 5 0 1 . 7 6 2 9 ( - 6 ,4 4 9 9 . 0 3 5 6 ~ 1 0 ,4 4 9 6 . 1 6 2 # 0 ,4 4 9 3 . , 4 6 0 ( - 2 ,4 4 6 9 . 9 6 4 9 ( - 1 6 ,4 4 6 6 . 6 6 1 5 ( - 1 7 ,4 4 6 3 . 2 3 6 2 ~ 2 0 ,


8/11

A%,-X22+ TRANSITION OF CP

TABLE I-Continued

R230.5 4476.4934,9,31.5 4472.63w,-28132.5 4468.6284,-9,33.5 4464.4862,42,34.5 -35.5 4455.7529,-3Qo)36.6 4451.1793,23)37.5 -36.5 4441.%346,-27,,9.5 4436.5x4,-4,40.5 4431.4189,-32,

p24xJ3.46083,8~4381.7892,-1334314.9774,55~4368.0136~21,4360.9101,634353.666zm4346.2aoo,-a~4338.7525(-17)4331.0859,-l,4323.2720(-4414315.3286,,2,

92 R2144,1.5088,9)442%2334,5)4420.8158,6)4415.*5344(-1514409.55OC-1114403.704%-21,4397.,182,-4,4391.5897,17,lw5.,151,3,4,78.8952,-39,4,72.,409~0~

4524.086X-12)4521.7553(8,4519.2736,-28,45!6.6516(-18)4513.6915,55,4510.9710(-25,4507.9145(-16,4504.71 l6,-22,4501.3667,314497.8735,-514494.2348,-163

4436.0796,21)443&927a,12,4425.6376(45,4420.1985( 15)4414.6194(12,44oa.a9a1,12,4403,0294~-36,4397.0277~ 12)4390.8776,1)4384.5852,-7,4378.1519,23

921

447%64r6(-10,4475.9106,-6,4472.034,~ I l4468.0098(-13)4463.84294368.5273,-39,4368.6251,9)4368.5%9,-47,436a.3422,-1214367.9654,-4,)4367.4369,-34,4366.,576,21)4365.9158,a)4364.9251160,4363.7&6,,-10)4362.4599,-9,4361.0035,50,4359.3794,-14,4357.6086,9)4355.6817,23,4353.5956(-134351.3%4,16,4348.9633,6,4346.4124,-121434,.7084,-9,4340.8484,-,6)43,7.8347,-1114,34.6661,-5143,1.3479(52)4,27.8678,38)4324.2338,32,432o.441a,-6,4,16.496,,-57,4312.x90,-41)4x)8.1531,14,4303.7449~-12)4299.1a95c32>4294.4795,72)4289.6057,14)4264.5828,4,4279.4079,12,4274.0811,,9~4268.5953,12,4262.9592,18)

4354.4362,-44)4351.4010,22,4346.2017,-114344.8468,-2614341.3451,28,4337.6817, I,,4333.8640,12)4329.8872,-35)4325.7691,5X4321.4aW-1914317.04ao~9~4312.4542,-12,43W7160,56)4302.81 TW6)4297.7541,-3414292.5&a,-10,4267.1890,6,4281.6692,-3514275.9999,-351427O.la!6(,2)4264.20,x-9,4258.0,,9,-5,4251.7898(-1614245.3540,-131423a.7652,-10)4232.0219,-2x4225.1275,-20)421a.oa4109,4210.8603~-22,1203.531% 1414196.0286,25,4166.3694,-a,4160.56a,-4,4!72.6OWa~4 164.4924( IO4156.2297,aI4147.8!39,-13,

43+%751oc49>4363.5883,-s)4362.2724,28,4360.7996,45,4359.1667,16)4,57.3779,-19,4355.4390,OI4353.3417,-12,4351.0949~34~44(8.6852,3)4X6.1230,-11434x4051,-IO,4340.5335,-5)4337.5to6,37,4334.3239,~9)43x).9892tm4327.4953,-n4323.8485,-9)4320.0482, I I4316.0908,-15143,1.9829,10)43W716Q,-IO,4303.2975,-3,4298.7237,-n429,.9954,-l,,4283.1 IN,-20)4284.079,,-2)4278.8897,-t)4273.543X-27,4268.0,90,-4,4262.3988,0)4256.59322(-16,4250.636,(-14,4244.5261,-6,423%2625,-a>4231.6525,5914225.2753,-19,42ta.5577,28)4211.6798,-J,4204.652X-2,

A2n,,2 - x3+ 3-l

RI Pl Q R12 PI2 9 1 23.5 8703.9bw-734.5 6703.2271,,6) 868x4396( I 6) 8689.5t95t-tn8687.83,7,-401


9/11

290 RAM AND BERNATHTABLE I-Continued

A211V2x3+ 3-l

RI P l Q1 R I 2 P I 2 9125 . 5 6 7 0 4 . 2 7 1 2 , - 4 6 ,6 . 5 6 7 0 5 . 1 2 7 1 , 2 17 . 5 6 7 0 5 . 7 7 9 4 , 2 8 )8 . 5 -9 . 5 8 7 0 6 . 4 7 3 3 ~ 1 6 ~

1 0 . 5 8 7 0 6 . 5 1 6 2 , - 9 11 1 . 5 8 7 0 6 . 3 6 2 1 , 1 1 ~1 2 . 5 8 7 0 6 . 0 0 5 5 ~ 2 1 ~1 3 . 5 8 7 0 5 . 4 4 7 8 , 3 4 )1 4 . 5 8 7 0 4 . 6 8 5 0 ~ 1 1 ~1 5 . 5 6 7 0 3 . 7 2 1 8 , O )1 6 . 5 8 7 0 2 . 5 6 0 4 , 2 1 )1 7 . 5 6 7 0 1 . 1 9 2 9 ( - 3 )1 6 . 5 8 6 9 9 . 6 1 6 9 , - 7 . 3 )1 9 . 5 -2 0 . 5 8 6 9 5 . 8 6 7 9 , - 1 2 12 1 . 5 8 6 9 3 . 7 1 9 7 , 1 6 )2 2 . 5 6 6 9 1 . 3 4 2 6 ( - 3 , )2 3 . 5 6 6 8 8 . 7 7 0 7 ( - 1 1 ,2 4 . 5 6 6 8 5 . 9 9 6 5 ( O )2 5 . 5 6 6 8 3 . 0 , 9 4 , - 4 )2 6 . 5 8 6 7 9 . 8 4 3 7 ~ 2 0 32 7 . 5 8 6 7 6 . 4 6 2 0 , - 3 12 6 . 5 8 6 7 2 . 8 7 5 7 , - 5 9 12 9 . 5 8 6 6 9. 1 0 0 5 , 1 0 )3 0 . 5 8 6 6 5 . 1 1 6 4 ~ 1 ~3 1 . 5 8 6 6 0 . 9 2 6 0 , - 5 6 )3 2 . 5 8 6 5 6 . 5 4 1 6 , - 4 5 )3 3 . 5 8 6 5 1 . 9 4 9 9 , - 9 4 )3 4 . 5 8 6 4 7. 1 7 3 1 , 1 7 )3 5 . 53 6 . 53 7 . 53 8 . 53 9 . 5

6 6 8 7 . 7 3 0 2 , - 3 8 )6 6 6 5 . 8 3 1 1 , 2 1 ~6 6 8 3 . 7 2 1 6 , - ( 2 )* 6 8 1 . 4 1 2 1 , - 4 0 ~6 6 7 8 . 9 1 3 6 , 5 3 )6 6 7 6 . 2 0 1 0 , 1 4 ~6 6 7 3 . 2 8 7 9 , - C ? , )6 6 7 0 . 1 7 6 6 , - 1 , )8 6 6 6 . 8 6 7 0 , 1 7 )6 6 6 3 . 3 5 4 3 , - 2 7 18 6 5 9 . 6 4 3 4 , - 1 2 )8 6 5 5 . 7 , 0 3 , - 1 4 )6 6 5 , . 6 1 8 7 , 4 )8 6 4 7 . 3 0 6 7 , 2 3 )8 6 4 2 . 7 9 5 6 ~ 5 7 ~6 6 3 &0 7 5 7 ( Z )6 6 3 3 . 1 5 6 4 ( - 2 3 )6 6 2 8 . 0 4 4 4 , - 1 3 )6 6 2 2 . 7 2 6 1 , - 4 5 ,6 6 1 7 . 2 1 6 5 , 1 0 ,8 6 1 1 . 5 0 2 1 , , 7 ,6 6 0 5 . 5 8 6 3 , 6 ,8 5 9 9 . 4 6 7 9 , - 3 0 18 5 9 3 . 1 5 5 4 , - l , )8 5 8 6 . 6 4 2 2 , - 4 )8 5 7 9 . 9 3 0 5 , 1 3 )8 5 7 3 . 0 1 4 3 < - 2 1 36 5 6 5 . 9 0 0 5 ( - 3 7 16 5 5 8 . 5 9 6 6 , 3 7 )6 5 5 1 . 0 6 8 2 ~ - , 4 3 18 5 4 3 . 3 7 6 , , 3 , )8 5 3 5 . 4 6 5 7 , 1 0 )8 5 2 7 . 3 6 2 1 , 4 5 )6 5 1 9 . 0 4 6 9 ( - 2 9 18 5 1 0 . 5 5 1 9 , 4 4 )

8 6 9 4 . 7 9 1 0 , 1 6 )6 6 9 4 . 0 6 3 2 , 2 0 )6 6 9 3 . , 3 4 4 , 2 2 ,6 6 9 1 . 9 9 6 7 , - 3 3 18 6 9 0 . 6 6 6 2 , - 4 5 ,6 6 a 9 . 1 3 6 6 , 5 ~6 6 6 7 . 4 0 6 5 , 1 6 )6 6 8 5 . 4 6 8 0 , - 2 4 ,8 6 6 3 . 3 3 6 6 , 1 8 ~6 6 8 0 . 9 9 8 7 , 4 ,667&4597(-l,)6 6 7 5 . 7 2 2 0 , - 4 )6 6 7 2 . 7 7 7 6 , - 5 3 )6 6 6 9 . 6 4 2 5 , - 5 )8 6 6 6 . 3 0 2 3 , 3 ,8 6 6 2 . 7 6 3 4 , 3 2 ,8 6 5 9 . 0 2 0 5 , 2 7 ,8 6 5 5 . 0 X4 , 1 6 )8 6 5 0 . 9 3 1 3 , 4 ,6 6 4 6 . 5 9 0 1 , 3 5 )6 6 4 2 . 0 4 1 9 , 2 ,8 6 3 7 . 3 0 0 , , 3 6 ,6 6 3 2 . 3 5 0 3 , - 5 )6 6 2 7 . 2 0 4 2 , - 6 16 6 2 1 . 8 5 9 1 , 5 )8 6 1 6 . 3 ! 1 6 , - 3 18 6 , 0 . 5 6 , 5 , - Z , )8 6 0 4 . 6 2 1 6 , 2 9 ,8 5 9 6 . 4 7 4 , , , 7 ,8 5 9 2 . , 2 5 0 ( - 9 16 5 8 5 . 5 8 2 0 ~ 2 4 ,8 5 7 8 . 6 3 4 6 ~ 1 1 ~6 5 7 1 . 6 8 5 0 ~ - 2 8 ). 9 5 6 4 . 7 4 3 7 , 1 2 )

8 6 9 4 . 9 0 9 5 , 1 )8 6 9 4 . 1 9 7 0 , - 3 0 18 6 9 3 . 2 8 7 0 , - 2 4 )6 6 9 2 . 1 7 6 9 , ~ 6 )8 6 9 0 . 8 6 4 0 , - 9 )6 6 6 9 . 3 5 3 1 ( 2 , )8 6 8 7 . 6 3 5 , ( - 1 0 )6 6 8 5 . 7 2 , 2 , , 2 )6 6 8 3 . 6 0 6 0 , 3 0 )6 6 6 1 . 2 6 2 8 , - 2 2 )8 6 7 8 . 7 6 5 2 , ~ 8 16 6 7 6 . 0 4 0 6 , - 5 5 18 6 7 3 . 1 2 4 2 ( - , , I6 6 7 0 . 0 0 7 6 , 4 0 16 6 6 6 . 6 6 4 6 , 3 7 ,6 6 6 3 . ! 5 7 4 , - 5 ,6 6 5 9 . 4 3 6 7 , Z . S6 6 5 5 . 5 0 7 X- 1 6 ,6 6 5 1 . 3 6 3 2 , - 8 ,8 6 4 7 . 0 5 8 1 , - l )8 6 4 2 . 5 3 3 9 , 2 1 )8 6 3 7 . 8 0 7 2 ~ 2 2 ~8 6 3 2 . 8 7 6 3 ( - 1 6 )6 6 2 7 . 7 5 2 0 , 1 6 )8 6 2 2 . 4 1 9 0 , - 3 6 )

8 6 1 1 . 1 7 0 2 , 3 6 ~8 6 0 5 . 2 3 7 9 , - 6 )6 5 9 9 . 1 0 6 5 , - 3 9 ,6 5 9 2 . 7 8 , 2 , - 1 2 16 5 8 6 . 2 5 6 5 ( , 9 )6 5 7 9 . 5 2 2 4 , - 4 7 ,6 5 7 2 . 5 9 9 1 , - 8 ,

6 6 7 1 . 2 3 7 5 ( 1 9 )6 6 6 7 . 3 7 2 4 ( 3 6 )6 6 6 3 . 2 9 7 4 , - 3 7 )8 6 5 9 . 0 2 0 5 , - 1 2 5 )6 6 5 4 . 5 6 5 0 , 5 ,6 6 4 9 . 8 9 2 9 , - 2 6 18 6 4 5 . 0 3 3 7 , 7 , ,8 6 3 9 . 9 5 3 4 , - 3 9 )8 6 3 4 . 6 8 9 2 , 1 4 )8 6 2 9 . 2 1 9 7 , 1 3 ~8 6 2 3 . 5 4 9 9 , 8 36 6 1 7 . 6 7 2 5 , - 7 5 16 6 1 1 . 6 0 9 6 , - 1 3 16 6 0 5 . 3 4 0 5 , - 2 2 18 5 9 8 . 8 7 1 7 , - 3 0 ,8 5 9 2 . 2 0 6 2 , 9 ~8 5 8 5 . 3 4 1 5 , 6 ~6 5 7 8 . 2 7 1 7 , - 3 2 )8 5 7 1 . 0 0 9 3 , - 6 ,6 5 6 3 . 5 5 1 4 , 5 , )6 5 5 5 . 6 8 6 O C? 3 ~6 5 4 8 . 0 2 0 6 , - 1 8 )6 5 3 9 . 9 6 6 3 , 3 8 38 5 3 1 . 7 0 0 3 , - 3 9 )8 5 2 3 . 2 5 1 6 , 4 2 )

8685.9495,3,8 6 8 3 . 8 6 3 0 , 1 3 )6 6 8 1 . 5 7 4 7 , 1 4 ~6 6 7 9 . 0 6 3 0 ( - 1 0 )8 6 7 6 . 3 9 2 5 ( - ! 3 )8 6 7 3 . 5 0 3 5 , 8 ,6 6 7 0 . 4 0 9 6 , - 1 1 ,8 6 6 7 . 1 2 0 0 , , 6 ~6 6 6 3 . 6 2 8 5 ( 3 4 )6 6 5 9 . 9 3 4 1 , 2 6 ,8 6 5 6 . 0 3 5 9 ( - 1 0 36 6 5 1 . 9 4 1 0 , - 9 )8 6 4 7 . 6 4 0 6 , - 5 7 18 6 4 3 . 1 5 3 0 , 2 3 )6 6 3 8 . 4 5 5 0 , , )6 6 3 3 . 5 5 5 6 , - 2 5 ,6 6 2 6 . 4 6 3 9 , 2 1 ,6 6 2 3 . 1 6 5 2 , O )8 6 1 7 . 6 7 3 6 , 5 0 )6 6 1 1 . 9 7 2 2 , 2 )8 6 0 6 . 0 7 7 5 , 1 9 ~6 5 9 9 . 9 7 9 3 , - 2 )6 5 9 3 . 6 8 2 6 , - ! O I6 5 6 7 . , 8 7 . 3 , - 4 ,8 5 8 0 . 4 6 6 7 , - 4 6 )8 5 7 3 . 5 9 9 6 , 7 ,6 5 6 6 . 5 0 2 2 ( - 3 , )6 5 5 9 . 2 1 2 6 ( Z )6 5 5 1 . 7 2 2 6 , 2 , )6 %4 . 0 3 l 4 , 1 8 )8 5 3 6 . 1 3 9 7 , O )

Note. The numbers in parentheses correspond to the observed minus calculated line positions (in 10m4cm-) using the spectroscopic constants of Tables II and III.

The rotational assignments of the five bands was straightforward using combinationdifferences and the previous estimates of the molecular constants (2-4). There are 12branches in each band and the notation appropriate for a 211-2Z transition is givenby Herzberg (15). The observed line positions are listed in Table I.

TABLE IIRotational Constants for the X22+ State of CP (in cm-; 1 SD in Parentheses)

1 0 %102X

T 0.0 1 2 2 6 . 1 2 7 3 ( 2 ) 2 4 3 8 . 5 7 4 3 ( 3 )% 0 . 7 9 5 8 8 1 6 ( 2 2 ) 0 . 7 8 9 8 9 5 5 ( 2 2 ) 0 . 7 8 3 8 9 4 4 ( 2 3 )DY 1 . 3 2 7 3 6 ( 8 3 ) 1 . 3 3 0 8 3 ( 6 4 ) 1 . 3 3 6 1 1 ( 9 0 )I " 1 . 8 5 4 3 9 ( 5 1 ) 1 . 8 5 0 0 6 ( 6 9 ) 1 . 8 4 5 4 9 , 7 7 )


10/11

A*&X22+ TRANSITION OF CP 2 9 1

TABLE IIIRotational Constants for the A211State of CP (in cm-; 1 SD in Parentheses)

constant v-0 v-1 v-3

T 6 8 8 4 . 0 0 5 6 ( Z )I c - 1 5 6 . 2 4 3 7 ( 2 )

1 0 5 X Ao y 4 . 8 5 6 ( , 8 )B" 0 . 7 0 9 2 7 6 9 ( 2 2 )

1 0 6 x o , 1 . 2 7 9 8 6 ( 8 2 )1 0 3 X k 9 . 4 1 1 ( 1 4 )1 0 5 x 4 " - 4 . 8 3 9 ( 4 7 )1 0 7 , p h - 1 . 2 0 < 11 )

7 934.4145(Z)- 1 5 6 . 1 2 6 9 ( 3 )

4 . 3 2 X3 5 )0 . 7 0 3 6 4 9 7 ( 2 2 )

1 . 2 8 2 3 9 ( 8 6 )9 . 4 3 8 ( 2 2 )

- 4 . 8 9 ( 1 1 )- 0 . 9 8 C L 8 )

9 999.0066(4)-155.89338

3 . 2 5 7 =0 . 6 9 2 3 6 4 4 ( 2 7 )

1 . 2 8 6 4 ( 1 3 )9 . 4 9 7 . a

- 5 . 1 9 ( 1 5 )- 0 . 5 4 a

a Fixed by extrapolation from u = 0 and 1. See text.

Band-by-band fits of the line positions of Table I were made utilizing the effectiveHamiltonian of Brown et al. (16). An explicit listing of the matrix elements for a IIand a 2Z+ state are given, for example, in a paper by Amiot et al. (17). For the finalfit all of the line positions of all of the bands (except 3-l for which a special fit wasmade) were fitted simultaneously to provide the molecular constants of Tables II andIII. Since only the 2113,2 pin component was observed in the 3-l band, the values ofAs, ADS, p3 and pn3 were estimated by extrapolation from u = 0 and 1 and fixed.Equilibrium molecular constants were derived from the data of Tables II and IIIand are displayed in Table IV. Since only three vibrational levels are available for theA% and X2X+ states, the vibrational and rotational constants of Table IV are an exactfit to the data. The quoted errors are derived by simple propagation of errors and arenot proper statistical errors. The neglect of weye almost certainly causes systematicerrors in w, and w&, far exceeding the quoted errors. From the B6 and Bg values theequilibrium bond distances of 1.561977(7) A for the X2Z+ state and 1.654421(7) Afor A211 are computed.

TABLE IVEquilibrium Molecular Constants for CP (in cm-)

0, 1 239.8076(5) 1 0 6 2 . 4 8 4 1 ( 5 )We % 6 . 8 4 0 X3 ) 6 . 0 3 7 6 ( Z )

Be 0 . 7 9 8 8 6 9 0 ( 3 6 ) 0 . 7 1 2 0 8 6 6 ( 2 8 )% 0 . 0 0 5 9 7 1 1 ( 5 5 ) 0 . 0 0 5 6 1 6 9 ( 3 5 )Ye - 0 . 0 0 0 0 0 7 5 ( 2 3 ) - 0 . 0 0 0 0 0 5 l 5 ( 7 * )' e ( A) 1 . 5 6 1 9 7 7 ( 7 ) 1 . 6 5 4 4 2 1 ( 7 )


11/11

292 RAM AND BERNATHThe Kratzer relationship (15) predicts 0: = 1.3267 X 10e6 cm- and Dk = 1.2794

X 10v6 cm- compared to the experimental values of 1.3256 X 10e6 and 1.2786 X 1Om6cm- for the X22+ and AII states, respectively. The Pekeris relationship (IS) predictscwg 0.005949 cm- and cr; = 0.005474 compared to the observed values of 0.00597 1and 0.005617 cm-.

The constants of Tables II-IV are in reasonable agreement with, but much moreaccurate and extensive than, those of Tripathi et al. (4) for the A211state. The agreementwith the X2x+ constants of Bihwald et al. (I) is also good except for the sign of y, thephenomenological spin-rotation constant. We concur with Tripathi et al. (4) that 7is positive. The signs and magnitudes of the A-doubling constants in the A211 stateand the spin-rotation constant in the XZ are similar to the values for the isostructuralmolecules CN (18) and SiN (19).

CONCLUSIONThe A211-X22+ transition of CP was observed with a high-resolution Fourier trans-

form spectrometer. This infrared electronic transition is the analog of the red systemof CN. The molecular constants may prove useful in the extraterrestrial detection ofphosphorus-containing molecules.

ACKNOWLEDGMENTSWe t h a n k R o b H u b b a r d a n d J e r e m yWa g n e r f or e x p e r t e c h n i c a l s s i st a n c en acquiring the CP spectrum

at Kitt Peak. This research was supported by the Office of N a v a l R e se a r c h .Ac k n o w l e d g e m e n t s a l so m a d et o t h e d o n o r s o f t h e P e t r o l e u mR e s e a r c hF u n d , a d m i n i st e r e d y t h e A CS , for partial supportof this work.RECEIVED: July 25, 1986

R E F E R E N C E S1. G. HERZBERG, at ure(London) 126, 131-132 (1930).2. H. BARWALD,G. HE RZBERG, ND L. HER ZBERG, n n . P h ys . 20,569-593 (1934).3. A. K. CHAUD HR YAN DK. N. UP ADHYA, nd. J. Phys. 43,83-9 1 (1969).4. R. TRI P ATHI, . B. RAI, AND K. N. UP ADHYA,Pramana 17,249-255 (1981).5. P . D. SINGHAN DA. N. P ATHAK, nd. J. Pure Appl. Phys. 7, 132- 133 (1969).6. T. WENTINKAN DR . J . S P I N D L E R ,. Quant. Spectrosc. Radiat. Transfer 10, 609-6 17 (1970).7. N. S. MURTHYAN DB. N. MUR THY,J. Phys. B 3, L15-Ll 8 (1970).8. N. S. MUR TH Y, L. S. GO WDA, AND B. N . MUR TH Y,Pramana 6,25-28 (1976).9. K. A. GINGERICH, hermochi m. Acta 2,233-236 (197 1) .

10. S. SMOES,C. E. MYER S,AN DJ . DROWART,Chem. Phys. Lett. 8, IO-12 (1971).II. J . KORDISAN DK. A. GINGER ICH, . Chem. Phy s. S&5058-5066 (1973).12. R. S. R AM AND P. F. BER NATH, . Mo l. Spectrosc. 122,275-281 (1987).13. G. GIJ ELACHVILI ,. Mol. Spectrosc. 75,25 l-269 (1979).14. J . R. ANACONA,P . B. DAVIES ,AN DP . A. HAMIL TON , 04,269-271 (1984).IS. G. HE RZBERG,S p e c t r a of Dia t omic Molecu les , 2nd ed., Van Nostrand-Reinhold, New York, 1950.16. J . M. BROWN,E. A. COLB OUR N, . K. G . WATSON,AMDF . D. WAYNE,J. Mol. Spectrosc. 74,294-3 18

(1979).17. C. AMIOT,J . P . MAILLARD,AN DJ . CHAUVILLE,. Mol. Spectrosc. 87, 196-2 18 (198 1).18. A. J . KOTLAR,R. W. F IELD, . I . STEINF ELD,NDJ . A. COXON,J . Mol . Spectrosc. 80, 86-108 (1980).19. S. C. F O S T E R ,K. G. LUBIC,AN DT. AMNO, J . Chem. Phy s. 82,709-713 (1985).

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R.S. Ram and P.F. Bernath- Fourier Transform Spectroscopy of the A^2-Pi-i-X^2-Sigma^+ System of CP

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