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The Herzberg system of 12C18O molecule
72, 297-300
JOURNALOFMOLECULARSPECTROSCOPY
(1978)
NOTES The
Herzberg
System of ‘*PO
Molecule
Systems of electronic levels in the CO molecule have been the subject of numerous investigations and monographs. However, until now higher levels of this molecule are known either partly or with little exactness. This is true for the CO molecule starting from C%f state up to all higher levels (1-4). Investigations of the C%+ state have hitherto been made by analyzing three band systems: the Herzberg system, formed as a result of C%+-AIB transition, the Hopfield-Birge system, generated in C’Z:+-X’Z+ transition, and the Knauss-system (only once mentioned), formed in CIZ’-a’%+ intercombination transition (I). The Herzberg system lies in the visible and near ultraviolet regions and forms a set of seven bands of O-r/ progression. So far it was basically analyzed only in the nYY0 molecule (5, 6). Some bands of this system were obtained in WrflO and trCt*O molecules, but such analysis was only fragmentary (7, 8). For this reason the present authors attempted a complete analysis of the bands of this system in the 12C180 molecule, with the aim to obtain the data for calculation of the C’Z+ state molecular constants and also to estimate possible occurrences of perturbations on the r~ = 0 level of the CIZ+ state of this molecule. The spectrum of the Herzberg system has been obtained in a hollow-cathode type lamp, with a graphite cathode. The lamp was filled with oxygen (containing 90% of l*Oz) under 3 Torr pressure, supplied with a SOOV dc generator, and a current of 40 mA. The bands were photographed in the 7-th to 4-th orders of a plane-grating Zeiss PGS-2 spectrograph (dispersion ranging 0.6 and 1.3 i/mm). Exposure time on 67A50 and 68A.56 Agfa-Geva-ert plates varied from 0.5 to 4 h. Iron standards from a hollow-cathode lamp were used as the comparison spectrum. The plates were measured on an Abbe-type comparator, and the wavenumbers of the lines were obtained using a computer program. The wavenumbers of the rotational structure of the measured bands are presented in Table I. The rotational constants of the C’Z+ state were computed by combining R(/) and P(J) lines and by forming A#‘(J) differences. On the basis of the least-squares method, using all the AzF’(J) values obtained from all the bands, the following constants are obtained :
B. = (1.85125 f 0.00007)
cm-‘;
Values for B, of the lower state in this transition bands by means of f*(J) function method (9) : Bf = (1.48400 f
0.00007)
B1 = (1.4410s f
O.OOOlr) cm-‘;
cm-t;
Do = (5.52 f
0.11) X 10-O cm-‘.
(4111) are determined
Ba = (1.46248 f and
in unperturbed
regions
of the
0.00012) cm-‘;
Bg = (1.41903 f
0.00013)
cm-r.
From the combination of the lines of the strongest bands, i.e., O-2 and O-3; O-2 and O-4; and O-2, and O-5 bands, the following differences of the rotational constants for AIII state have been calculated by Jenkins and McKellar method (10) : B1 -
BB = (0.02190
f
0.00007) Bz -
cm+;
BP -
Bs = (0.06521
f
B1 = (0.04332 f 0.00013)
0.00006)
cm-r;
and
cm-l.
Using the above set of rotational constants for A1II state, a set of seven equations for B, and (Ye(assuming Ye = 0), was solved by the least-squares method. The following constants were obtained: B, = (1.5385 f
0.0002)
cm-r;
a, = (0.012170
f
0.00005)
cm-‘.
297 0022.2852/78/0122-0297$02.00/O Copyright @ 1978 by Academic Press, Inc. All rights of reproduction in any form reserved.
1 2 3 4 5 6
: 9 10 11 12 13 14 15 16 17 18 19 20
-
J
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
1
J
0
.292?.ii 924.94* 92?.27 Y3L.37 334.2b 936.87" 944.37 950.58 957.57 365.35 4?3.92* 353.2'1 993.34 .SU4.?3 026.37 WI.63 J5L.7;
Q
o-3 ~___
27161.15' 160.30' *
P
985.1. i,,z,- 2-
lb9.61* 16i.:s* 152.57 156.77 160.30 163.93 168.06 172.95 :74.co* 175.13 183.94 192.03 200.11 208.57 217.57 227.20 237.48 248.57*
Lil?iS.b5' 31;.55x 916.ib 915.56 ?I'.74 41L.iU 918.45 920.36 924.21 '1LP.d' 131.ic ?IR.R7X 345.21 952.E; 9611.L3 369.1'3 ?!P.ii
P
27169.241 171.27' 174.06* 177.57 181.87* 197.02 193.261 200.84 183.19 210.37 193.26" 222.23* 202.94' 236.34' 212.31 221.72 231.43 241.60* 252.32 263.61* 275.54* 288.11' 301.29' 315.16" 329.93
Q
0 -
!?i.PA _7(3. 14li.it, ,hr.,l lh.3.7 ‘..“1.
22336.04X 942.06 948.86 956.46 364.85 973.9?" 983.89 994.57 21006.05 018.24 331.31 345.09 059.69 075.0: 091.18 13108.1;
R
.-_____
27186.24* 192.90* 200.44* 190.59* 197.89' 209.26 208.16* 219.70 230.63 241.60* 253.15 265.42* 278.83 282.37* 298.55 314.02 329.53x 345.29 361.6?
R
TABLE
I
I
873.32 888.93 T5935.16 921.97' 939.55 957.85
25735.67" 747.14 749.271 751.22x 165.77 775.03 785.39 795.65 25807.02 819.13 832.05 846.6, 858.28
R
Q
1
*
2581I.03 823.17* 834.39 * 662.06 876.58 891.84
'/23.6'+ 127.13 T31.30 736.16 741.74 748.01* /55.04* 762.87 7f~ii.22 773.CT 779.47 789.35 199.83
25717.39” 718.75
0
Wavenumbers of the Rotational Lines of the Bands in C’Z+-A’rl
768.43 177.95 785.18' 799.06* 15810.74"
751.34
i5711.36" 109.75 708.82* 708.61 709.07 710.25 712.12 714.68 717.95 721.93 726.65 732.19 739.35* 1
P
Q
Q
O-6
4304.48' 305.39" 308.14 311.09 314.76 319.18 324.35* 329.93 336.68 344.04 352.11 360.92 370.46 380.75 391.77 403.53 416.02 429.27 143.26 457.38 1473.46 489.73
o-2 P
P
24300.53' 298.35 296.9S1 296.24' 296.24' 296.95+ 298.35 300.53 303.44' 307.08 311.46 316.57' 322.43 329.02 336.34 344.42 353.25 362.81 373.13 384.2: 396.07 408.73
:sy77.29* 37y.15* 987.0:" 169iI.31' 190,.1_,.3b* 985.tiR 97:.01, 1.::i* 990.65 972.08' ili2.;5* 996.ih 974.02 "32.36X ;91111>.:5* 376.86 %j.50* ClO.18 980.59 J5S.?ih 318.49 985.18 968.3" fl2i.b'i 990.65 082.:“ 1;37.?3 997.25 3'1U.,:! :9oc4.3t? 096.62* 19?:1.:+7* 'Jli.58 36C.6: lL8.93 073.411 J21.68 ;16.ji 1167.li L'V.bB :'111)/.7G ib4.6,i 042.bl I1i.i' 354.x 1‘31.8t*
R
345.05 353.89X 363.44 373.73 384.77 396.53 409.04 422.28 436.26 450.96 466.41 482.59 Li99.51 517.20 525.63 554.82 574.8h
336.95f
24322.94 329.56
R
Transition (cm-‘)
299
NOTES TABLE Band Origins
for the C%+-ArII
II
System
of lzC’sO Molecule
Method of obtaining
BEXld
REMARKS Perturbed in origin e32state Perturbed in origin
o-o
27167.1+0.1
Q-branch
o-1
25716.67kO.02
Q-branch
o-2
24303.744+0.010
Q-branch
o-3
22922.605+0.005
Q-branch and g-function
o-4
21574.898
Q-branch and g-function
o-
5
O-6
+~I.008
d'A
20260.47 to.01
Q-branch and g-function
18976.30
Q-branch
to.03
(cm-‘)
by by
state
Perturbed in origin by state (probably)
d3A
These constants are in good agreement with the values calculated on the basis of the Rytel data (II, 12). Values of differences of the band origins for respective bands are also calculated by Jenkins and McKellar method :
~~2- co3= (1381.136 f 0.007) cm-i; 402 -
co2 -
~0~ = (2728.831
00~ = (4043.262 f
f
0.010) cm-r;
and
O.Ols) cm-r.
Absolute values of band origins were calculated for all the bands by extrapolation of Q-branch lines by using g,(J) functions (9). These calculations were performed on unperturbed band parts and for low values of J values. Results and corresponding remarks are listed in Table II. The obtained results also allowed us to decide on the existence of perturbations in CiZ+. For this purpose behavior of the following expression : AzFo’J/J
+ ) = 4Bo -
6Do -
8Do(J + +)”
has been analyzed as a function of (J + 4)’ and its regular and linear course was obtained. Therefore in spite of the report of perturbation existence in the near BZ+ state (13) we regard the D = 0 level in CrZ+ state of r*CisO molecule as unperturbed within the limits of experimental error. ACKNOWLEDGMENT This work was financially
supported
by a grant
from the Union of Scientific
Work of SAP Vojvodina.
REFERENCES NSRD-NBS No. 5, Washington, 1. P. H. KRUPENIE, “The Band Spectrum of Carbon Monoxide,” 1966. 2. B. ROSEN, “Donnees Spectroscopiques Relatives aux Molecules Diatomique.” Pergamon Press, Oxford, 1970. 3. S. G. TILPORD, J. D. SIMMONS, J. Phys. Chem. Ref. Data 1, 147 (1972). 4. J. JANJI~, “Investigation of Electronic Molecular Spectra of i2Ci*0 and 12C1*O+ molecules” (Ph.D. Thesis), University of Novi Sad, 1972. 5. R. C. JOHNSON AND R. K. ASUNDI, Proc. Roy. Sot. 123, 560 (1929). 6. R. SCHMID, L. GERG, Z. Phys. 93, 656 (1935). 7. R. K. ASUNDI, J. Mol. Spectrosc. 34, 528 (1970). 8. R. KFPA, Ada Phys. Polon. A-36, 1109 (1969). 9. I. KovAcs, “Rotational Structure in the Spectra of Diatomic Molecules,” AkadCmiai kiad6, Budapest, 1969. New York, 1950. 10. G. HERZBERG, “Spectra of Diatomic Molecules, ” 2nd Ed., Van Nostrand, 11. M. RYTEL, Acta Phys. Polon. A-38. 299 (1970).
NOTES
300
12. M. RYTEL, “Uklad r\ngstriima w widmach izotopowich drobin CO,” &print 123, TO&I, 13. J. JANJI~, J. DANIELAK, R. KEP:\, .~E;DM. RYTEL, Acta Phys. Polorz. A-41, 7.57 (1972).
1970.
Z~tslitutc of Physics Faculty of Nata~al Scieltces University of Novi Sad 21000 Novi Sad, Yugoslavia Boris Kidrit Institz~le Vi&a-Beograd 11000 Beograd, Yqosiuvia K. KFP” M. RYTEL Atomic and Molecular Pedagogical College RzeszBw, Poland
Physics Laboratory
Received: November 28. 1977
JOURNALOFMOLECULARSPECTROSCOPY
(1978)
NOTES The
Herzberg
System of ‘*PO
Molecule
Systems of electronic levels in the CO molecule have been the subject of numerous investigations and monographs. However, until now higher levels of this molecule are known either partly or with little exactness. This is true for the CO molecule starting from C%f state up to all higher levels (1-4). Investigations of the C%+ state have hitherto been made by analyzing three band systems: the Herzberg system, formed as a result of C%+-AIB transition, the Hopfield-Birge system, generated in C’Z:+-X’Z+ transition, and the Knauss-system (only once mentioned), formed in CIZ’-a’%+ intercombination transition (I). The Herzberg system lies in the visible and near ultraviolet regions and forms a set of seven bands of O-r/ progression. So far it was basically analyzed only in the nYY0 molecule (5, 6). Some bands of this system were obtained in WrflO and trCt*O molecules, but such analysis was only fragmentary (7, 8). For this reason the present authors attempted a complete analysis of the bands of this system in the 12C180 molecule, with the aim to obtain the data for calculation of the C’Z+ state molecular constants and also to estimate possible occurrences of perturbations on the r~ = 0 level of the CIZ+ state of this molecule. The spectrum of the Herzberg system has been obtained in a hollow-cathode type lamp, with a graphite cathode. The lamp was filled with oxygen (containing 90% of l*Oz) under 3 Torr pressure, supplied with a SOOV dc generator, and a current of 40 mA. The bands were photographed in the 7-th to 4-th orders of a plane-grating Zeiss PGS-2 spectrograph (dispersion ranging 0.6 and 1.3 i/mm). Exposure time on 67A50 and 68A.56 Agfa-Geva-ert plates varied from 0.5 to 4 h. Iron standards from a hollow-cathode lamp were used as the comparison spectrum. The plates were measured on an Abbe-type comparator, and the wavenumbers of the lines were obtained using a computer program. The wavenumbers of the rotational structure of the measured bands are presented in Table I. The rotational constants of the C’Z+ state were computed by combining R(/) and P(J) lines and by forming A#‘(J) differences. On the basis of the least-squares method, using all the AzF’(J) values obtained from all the bands, the following constants are obtained :
B. = (1.85125 f 0.00007)
cm-‘;
Values for B, of the lower state in this transition bands by means of f*(J) function method (9) : Bf = (1.48400 f
0.00007)
B1 = (1.4410s f
O.OOOlr) cm-‘;
cm-t;
Do = (5.52 f
0.11) X 10-O cm-‘.
(4111) are determined
Ba = (1.46248 f and
in unperturbed
regions
of the
0.00012) cm-‘;
Bg = (1.41903 f
0.00013)
cm-r.
From the combination of the lines of the strongest bands, i.e., O-2 and O-3; O-2 and O-4; and O-2, and O-5 bands, the following differences of the rotational constants for AIII state have been calculated by Jenkins and McKellar method (10) : B1 -
BB = (0.02190
f
0.00007) Bz -
cm+;
BP -
Bs = (0.06521
f
B1 = (0.04332 f 0.00013)
0.00006)
cm-r;
and
cm-l.
Using the above set of rotational constants for A1II state, a set of seven equations for B, and (Ye(assuming Ye = 0), was solved by the least-squares method. The following constants were obtained: B, = (1.5385 f
0.0002)
cm-r;
a, = (0.012170
f
0.00005)
cm-‘.
297 0022.2852/78/0122-0297$02.00/O Copyright @ 1978 by Academic Press, Inc. All rights of reproduction in any form reserved.
1 2 3 4 5 6
: 9 10 11 12 13 14 15 16 17 18 19 20
-
J
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
1
J
0
.292?.ii 924.94* 92?.27 Y3L.37 334.2b 936.87" 944.37 950.58 957.57 365.35 4?3.92* 353.2'1 993.34 .SU4.?3 026.37 WI.63 J5L.7;
Q
o-3 ~___
27161.15' 160.30' *
P
985.1. i,,z,- 2-
lb9.61* 16i.:s* 152.57 156.77 160.30 163.93 168.06 172.95 :74.co* 175.13 183.94 192.03 200.11 208.57 217.57 227.20 237.48 248.57*
Lil?iS.b5' 31;.55x 916.ib 915.56 ?I'.74 41L.iU 918.45 920.36 924.21 '1LP.d' 131.ic ?IR.R7X 345.21 952.E; 9611.L3 369.1'3 ?!P.ii
P
27169.241 171.27' 174.06* 177.57 181.87* 197.02 193.261 200.84 183.19 210.37 193.26" 222.23* 202.94' 236.34' 212.31 221.72 231.43 241.60* 252.32 263.61* 275.54* 288.11' 301.29' 315.16" 329.93
Q
0 -
!?i.PA _7(3. 14li.it, ,hr.,l lh.3.7 ‘..“1.
22336.04X 942.06 948.86 956.46 364.85 973.9?" 983.89 994.57 21006.05 018.24 331.31 345.09 059.69 075.0: 091.18 13108.1;
R
.-_____
27186.24* 192.90* 200.44* 190.59* 197.89' 209.26 208.16* 219.70 230.63 241.60* 253.15 265.42* 278.83 282.37* 298.55 314.02 329.53x 345.29 361.6?
R
TABLE
I
I
873.32 888.93 T5935.16 921.97' 939.55 957.85
25735.67" 747.14 749.271 751.22x 165.77 775.03 785.39 795.65 25807.02 819.13 832.05 846.6, 858.28
R
Q
1
*
2581I.03 823.17* 834.39 * 662.06 876.58 891.84
'/23.6'+ 127.13 T31.30 736.16 741.74 748.01* /55.04* 762.87 7f~ii.22 773.CT 779.47 789.35 199.83
25717.39” 718.75
0
Wavenumbers of the Rotational Lines of the Bands in C’Z+-A’rl
768.43 177.95 785.18' 799.06* 15810.74"
751.34
i5711.36" 109.75 708.82* 708.61 709.07 710.25 712.12 714.68 717.95 721.93 726.65 732.19 739.35* 1
P
Q
Q
O-6
4304.48' 305.39" 308.14 311.09 314.76 319.18 324.35* 329.93 336.68 344.04 352.11 360.92 370.46 380.75 391.77 403.53 416.02 429.27 143.26 457.38 1473.46 489.73
o-2 P
P
24300.53' 298.35 296.9S1 296.24' 296.24' 296.95+ 298.35 300.53 303.44' 307.08 311.46 316.57' 322.43 329.02 336.34 344.42 353.25 362.81 373.13 384.2: 396.07 408.73
:sy77.29* 37y.15* 987.0:" 169iI.31' 190,.1_,.3b* 985.tiR 97:.01, 1.::i* 990.65 972.08' ili2.;5* 996.ih 974.02 "32.36X ;91111>.:5* 376.86 %j.50* ClO.18 980.59 J5S.?ih 318.49 985.18 968.3" fl2i.b'i 990.65 082.:“ 1;37.?3 997.25 3'1U.,:! :9oc4.3t? 096.62* 19?:1.:+7* 'Jli.58 36C.6: lL8.93 073.411 J21.68 ;16.ji 1167.li L'V.bB :'111)/.7G ib4.6,i 042.bl I1i.i' 354.x 1‘31.8t*
R
345.05 353.89X 363.44 373.73 384.77 396.53 409.04 422.28 436.26 450.96 466.41 482.59 Li99.51 517.20 525.63 554.82 574.8h
336.95f
24322.94 329.56
R
Transition (cm-‘)
299
NOTES TABLE Band Origins
for the C%+-ArII
II
System
of lzC’sO Molecule
Method of obtaining
BEXld
REMARKS Perturbed in origin e32state Perturbed in origin
o-o
27167.1+0.1
Q-branch
o-1
25716.67kO.02
Q-branch
o-2
24303.744+0.010
Q-branch
o-3
22922.605+0.005
Q-branch and g-function
o-4
21574.898
Q-branch and g-function
o-
5
O-6
+~I.008
d'A
20260.47 to.01
Q-branch and g-function
18976.30
Q-branch
to.03
(cm-‘)
by by
state
Perturbed in origin by state (probably)
d3A
These constants are in good agreement with the values calculated on the basis of the Rytel data (II, 12). Values of differences of the band origins for respective bands are also calculated by Jenkins and McKellar method :
~~2- co3= (1381.136 f 0.007) cm-i; 402 -
co2 -
~0~ = (2728.831
00~ = (4043.262 f
f
0.010) cm-r;
and
O.Ols) cm-r.
Absolute values of band origins were calculated for all the bands by extrapolation of Q-branch lines by using g,(J) functions (9). These calculations were performed on unperturbed band parts and for low values of J values. Results and corresponding remarks are listed in Table II. The obtained results also allowed us to decide on the existence of perturbations in CiZ+. For this purpose behavior of the following expression : AzFo’J/J
+ ) = 4Bo -
6Do -
8Do(J + +)”
has been analyzed as a function of (J + 4)’ and its regular and linear course was obtained. Therefore in spite of the report of perturbation existence in the near BZ+ state (13) we regard the D = 0 level in CrZ+ state of r*CisO molecule as unperturbed within the limits of experimental error. ACKNOWLEDGMENT This work was financially
supported
by a grant
from the Union of Scientific
Work of SAP Vojvodina.
REFERENCES NSRD-NBS No. 5, Washington, 1. P. H. KRUPENIE, “The Band Spectrum of Carbon Monoxide,” 1966. 2. B. ROSEN, “Donnees Spectroscopiques Relatives aux Molecules Diatomique.” Pergamon Press, Oxford, 1970. 3. S. G. TILPORD, J. D. SIMMONS, J. Phys. Chem. Ref. Data 1, 147 (1972). 4. J. JANJI~, “Investigation of Electronic Molecular Spectra of i2Ci*0 and 12C1*O+ molecules” (Ph.D. Thesis), University of Novi Sad, 1972. 5. R. C. JOHNSON AND R. K. ASUNDI, Proc. Roy. Sot. 123, 560 (1929). 6. R. SCHMID, L. GERG, Z. Phys. 93, 656 (1935). 7. R. K. ASUNDI, J. Mol. Spectrosc. 34, 528 (1970). 8. R. KFPA, Ada Phys. Polon. A-36, 1109 (1969). 9. I. KovAcs, “Rotational Structure in the Spectra of Diatomic Molecules,” AkadCmiai kiad6, Budapest, 1969. New York, 1950. 10. G. HERZBERG, “Spectra of Diatomic Molecules, ” 2nd Ed., Van Nostrand, 11. M. RYTEL, Acta Phys. Polon. A-38. 299 (1970).
NOTES
300
12. M. RYTEL, “Uklad r\ngstriima w widmach izotopowich drobin CO,” &print 123, TO&I, 13. J. JANJI~, J. DANIELAK, R. KEP:\, .~E;DM. RYTEL, Acta Phys. Polorz. A-41, 7.57 (1972).
1970.
Z~tslitutc of Physics Faculty of Nata~al Scieltces University of Novi Sad 21000 Novi Sad, Yugoslavia Boris Kidrit Institz~le Vi&a-Beograd 11000 Beograd, Yqosiuvia K. KFP” M. RYTEL Atomic and Molecular Pedagogical College RzeszBw, Poland
Physics Laboratory
Received: November 28. 1977