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Infrared combination bands of 12C2H2 involving 0000011 state
JOURNAL
OF MOLECULAR
SPECTROSCOPY
48, 600-603
(1973)
NOTES Infrared
Combination
Bands of 12C,H, Involving
00ooO1’ State
In the region of about 4100 cm-i (2.4 p) the acetylene spectrum is mostly due to “I + ~5~and its associated “hot” bands originating from the levels 114= 1 (000110~) and 216= 1 (0000”11) in the ground electronic state. From a study of the emission spectrum of acetylene observed with a grille spectrometer, Delaval, Cartigny and Lecomte (I) identified six bands in this region and on the basis of their measurements they were able to determine some of the vibrational constants. Most of these constants have the same orders of magnitude compared to the ones evaluated from the acetylene bands in other spectral regions except for the constant ~55 which differs considerably from the value derived on the basis of studies of the 15 micron spectrum of acetylene (.2,3). The present study has been undertaken to resolve this discrepancy and evaluate the rotational constants for the levels involved. The previous high resolution absorption work of Wiggins, Plyler, and Tidwell (4) at 2.4~ was mainly confined to the investigation of the combination band ~1 + ~5’ and, therefore, it was not possible to reanalyze the absorption data to correlate the results with the emission results. The experimental procedures adopted here are the same as those described in previous publications from this laboratory. The energy levels and the rotational constants resulting from this study are summarized in Table I and the observational data (with accuracy of about f0.005 cm-l) on which they are based are given in Tables II-IV.
-7.040
e 5
-2.239
f
5
-7.166 f 15
(1001’1’)~
(4
) ”
(1001’1’)~ (T‘) ”
(1001~1’)~ (Zf) ”
1000~22
CAB)
0001’0~ -1.936 f 4 -7.05
0001’0~
t 3
-6.43
f 3
-2.17
i 3
0001’0~
OOOOQ11 mu)
-7.132 i 15 -7.09
muI
0100~3’
UT”)
i 2
-1.16
000&Q
$1
? 5
-1.76
i 3
-6.82
f 3
-4.09
f 8
5.30
k 4
'k'%H? 1OOOQl'
Copyright All rights
(n)
0000w
Q 1973 by Academic of reproduction
-6.655 f 17
v+>
Press.
in any form
-2.065 t 5
Inc. reserved.
4173.349
4169.810
+ Blended lines
10 11 12 13 14 15 16 17 1s 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
9
a
4093.511 4095.847
0 1 2 3 4 5 6 7
4098.152 4100.439 4102.735 4105.003 4107.246 4109.499 4111.723 4113.920 4116.129 4118.303 4120.464 4122.628 4124.755 4126.876 4128.996 4131.077 4133.166 4135.230 4137.275 4139.322 4141.330 4143.343 4145.324 4147.307 4149.265 4151.207 4153.143 4155.045 4156.957 4158.828 4160.707 4162.550 4164.403 4166.211
R(J)OBS.
J
4086.454 4084.064 4081.670 4079.269 4076.843 4074.402 4071.953 4069.943 4067.018 4064.516 4062.012 4059.500 4056.970 4054.423 4051.857 4049.281 4046.697 4044.102 4041.494 4038.869 4036.234 4033.563 4030.893 4028.216 4025.524 4022.825 4020.105 4017.377 4014.626 4011.877 4Go9.101 4006.323 4003.533 4wo.713 3997.891
P(J)OBS.
4087.915
4090.975 4090.930 4090.872 4090.824 4090.764 4090.701 4090.633 4090.559 4090.482 4090.400 4090.313 4090.219 4090.126 4090.026 4089.917 4089.811 4089.691 4089.575 4089.452 4089.322 4089.IM 4089.047 4088.9O?f 4088.744 4088.592 4088.427 4088.261
4091.051
qmoas.
12C12CH* (looo”l’) - (ooco”oo)
12C12CH2
4179.598
4143.565 4145.883 4148.197 4150.520 4152.819 4155.106 4157.389 4159.648 4161.908 4164.167 4166.398 4168.631 4170.856 4173.052 4175.250
R(J,OBS.
4087.567 4085.033 4082.530
4102.657 4100.148 4097.641 4095.142 4092.609
4122.228 4119.808 4117.378 4114.956 4112.519 4110.062
4131.788 4129.421 4127.013
P(J)OBS.
4141.930
4139.034 4139.095 4139.164 4139.247 4139.322 4139.426 4139.537 4139.656 4139.774 4139.902 4140.036 4140.175 4140.329 4140.483 4140.645 4140.806 4140.975 4141.148 4141.330 4141.539
4138.938
4138.898
QWOSS.
(01co"31) - vmc0ooo)
W2C”
4113.833 4115.905 4117.948 4119.984 4122.011 4124.004 4125.993 4127.974 4129.956 4131.903
4109.664
4101.141 4103.301 4105.441
4092.428 4094.624 4096.813
4081.197 4083.473 4085.742 4087.970
R(J)OBS.
4020.200 4017.605 4014.977 4012.335 4009.695 4007.043
4040.599 4038.100 4035.581 4093.042 4030.487 4027.935
4050.496 4048.041 4045.571
4067.305 4064.935 4062.564 4060.181 4057.774 4055.368
P(J)OBS.
4078.704 4078.652 4078.603 4078.555 4078.496 4078.429 4078.39x 4078.302 4078.214t 4078.148 4078.060 4077.992t 4077.886 4077.784+ 4077.690 4077.566+ 4077.476
Q(J)OSS.
(looool') - (OE0ooOO)
;: 33 34 35 36 37
G 29 30
::
:; 20 21 22 23 24
2 7 a 9 10 11 12 13 14 15 16 17
2 3 4
0 1
.I
NOTES
602
(1”“11,1)*-(0001’0”) d-d
1 2 3 4 5 6 7 8 9 1” 11 12 13 14
4081.812 4084.128 4086.454 4088.144 4091.027 4093.272 4095.527 4097.741 4099.96” 4102.173 4104.348 4106.525 4108.685 4110.818
4067.615 4065.19” 4062.77” 4060.326 4057.862 4055.368 4052.901 4050.401 4047.886 4045.354 4042.805 4040.248 4037.682 4035.103 4032.505 4029.887 4027.258 4024.618 4021.964 4”,9.,“6 4016.643 4013.94” 4”,1.241 4005.804 4003.064 4”““. 285
+ Blended
4080.332 4082.681 4084.969 4087.256
4077.038 4076.971 4076.882 4076.843 4076.797 4076.737 4076.683 4076.621 4076.553 4076.48” 4076.411 4076.332 4076.25” 4076.17” 4076.081 4075.984 4075.884 4075.791
(1”“1111)“-(“0”11”“)
dtd
4091 .*a0 ‘“94.041 4096.279 4098.497 4100.691 4102.892
cc-c
4068.537 4061.8”” 4061.732 4061.653 4061.547t 4061.453 4061.333 1061.197 4061.05” 4060.875 4060.69” 4060.489 4060.267 4060.032 4059.768
4063.724 4061.29” 4058.852 4056.391 4053.929 4051.433 4048.927
4059.174 4058.852 4058.514 4058.15”
4075.567
lines
4073.248 4070.902 ‘“68.537 4066.167 4063.794 4061.406 4059.018 ‘“56.642 4054.256 4051.857 4049.45‘3 4047.074 4044.694 4042.299 4039.907 4037.526 4035.103
+ Blended
(1”“1~1’)“- (“o”11”“3 dtc
lines
4017.992 4080.332 4082.681 4080.149 4080.075 4079.968 4079.846 4079.73, 4079.604 4079.453 4079.314
4087.334 4091.959 4094.227+ 4096.556 4098.842 4101.123
4 5 6 7 8 9 1” 11 12 13 14 15 16 17 18 19 2” 21 22 23
NOTES
-
603
FIG. 1. Effects of perturbations in iZCxH~ bands. Erratum: The labeling of the band ~1 + (~4 + Y#’ Y,,’ is erroneously given as Y~(Y( + Y# - ~4~in the left half of the figure.
The main conclusions reached in the present work are summarized below. The molecular constants determined are consistent with the information obtained from the experimental data for nearly thirty other bands of acetylene studied in this laboratory. The spectral resolution available at 2.4 p allowed the observation of Q branch structures in addition to the R and P branches and therefore, we could study the molecular constants in greater detail. This was not possible in the case of the emission work (1). Second, the observational effect of perturbations in states where the 214= 1 and 210= 1 levels are simultaneously excited are similar to those observed earlier (5, 6). These effects are clearly evident from the reproduction shown in Fig. 1 where the appropriate combination relations are plotted. Finally, we find that the gj:, constant is correct as in Refs. _ 3 and 3 and the difference from the determination in Ref. 1 is probably due to the way in which this constant has been defined in that work. ACKNOWLEDGMENTS The financial support extended by the C. N. R., Italy is gratefully acknowledged. One of us (K. N. R.) would like to express his thanks for the part support extended this research by the National Science Foundation. REFERENCES 1. Y. DELAVAL, J. CARTIGNY, ANDJ. LECOMTE, Volume Jubilaire Louis d’Or, Memoire Hors Serie de la SociCt6 Royale des Sciences de Liege, Belgium, pp. 65-74 (1971). 2. K. F. PALMER, M. E. MICKELSON, AND K. NARAHARIRAO, J. Mol. Spectrosc. 44, 131 (1972); see K. F. PALMER, Ph.D. dissertation, The Ohio State University, 1972 for more details. 3. J. PLfVA, J. Mol. Speclrosc. 44, 165 (1972). 4. T. A. WIGGINS, E. K. PLYLER, ANDE. D. TIDWELL, J. Opt. Sot. Amer. 51, 1219 (1961). 5. K. F. PALMER, S. GHERSETTI, ANDK. NARAHARIRAO, J. Mol. Spectrosc. 30, 146 (1969). 6. A. BALDACCI,S. GHERSETTI, ANDK. NARAHARIRAO, J. Mol. Spectrosc. 34, 3.58 (1970). Ueparlment of Organic Chemistry Universily of Venke CaUe Larga S. Marta 2137 verresti (Italy) I)eparlment cf Physics The Ohio State University Colmbus, Ohio 43210 Received: June 1, 1973
AGOSTINO BALDACCI SERGIO GHERSETTI
K. NARAHARI RACI
OF MOLECULAR
SPECTROSCOPY
48, 600-603
(1973)
NOTES Infrared
Combination
Bands of 12C,H, Involving
00ooO1’ State
In the region of about 4100 cm-i (2.4 p) the acetylene spectrum is mostly due to “I + ~5~and its associated “hot” bands originating from the levels 114= 1 (000110~) and 216= 1 (0000”11) in the ground electronic state. From a study of the emission spectrum of acetylene observed with a grille spectrometer, Delaval, Cartigny and Lecomte (I) identified six bands in this region and on the basis of their measurements they were able to determine some of the vibrational constants. Most of these constants have the same orders of magnitude compared to the ones evaluated from the acetylene bands in other spectral regions except for the constant ~55 which differs considerably from the value derived on the basis of studies of the 15 micron spectrum of acetylene (.2,3). The present study has been undertaken to resolve this discrepancy and evaluate the rotational constants for the levels involved. The previous high resolution absorption work of Wiggins, Plyler, and Tidwell (4) at 2.4~ was mainly confined to the investigation of the combination band ~1 + ~5’ and, therefore, it was not possible to reanalyze the absorption data to correlate the results with the emission results. The experimental procedures adopted here are the same as those described in previous publications from this laboratory. The energy levels and the rotational constants resulting from this study are summarized in Table I and the observational data (with accuracy of about f0.005 cm-l) on which they are based are given in Tables II-IV.
-7.040
e 5
-2.239
f
5
-7.166 f 15
(1001’1’)~
(4
) ”
(1001’1’)~ (T‘) ”
(1001~1’)~ (Zf) ”
1000~22
CAB)
0001’0~ -1.936 f 4 -7.05
0001’0~
t 3
-6.43
f 3
-2.17
i 3
0001’0~
OOOOQ11 mu)
-7.132 i 15 -7.09
muI
0100~3’
UT”)
i 2
-1.16
000&Q
$1
? 5
-1.76
i 3
-6.82
f 3
-4.09
f 8
5.30
k 4
'k'%H? 1OOOQl'
Copyright All rights
(n)
0000w
Q 1973 by Academic of reproduction
-6.655 f 17
v+>
Press.
in any form
-2.065 t 5
Inc. reserved.
4173.349
4169.810
+ Blended lines
10 11 12 13 14 15 16 17 1s 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
9
a
4093.511 4095.847
0 1 2 3 4 5 6 7
4098.152 4100.439 4102.735 4105.003 4107.246 4109.499 4111.723 4113.920 4116.129 4118.303 4120.464 4122.628 4124.755 4126.876 4128.996 4131.077 4133.166 4135.230 4137.275 4139.322 4141.330 4143.343 4145.324 4147.307 4149.265 4151.207 4153.143 4155.045 4156.957 4158.828 4160.707 4162.550 4164.403 4166.211
R(J)OBS.
J
4086.454 4084.064 4081.670 4079.269 4076.843 4074.402 4071.953 4069.943 4067.018 4064.516 4062.012 4059.500 4056.970 4054.423 4051.857 4049.281 4046.697 4044.102 4041.494 4038.869 4036.234 4033.563 4030.893 4028.216 4025.524 4022.825 4020.105 4017.377 4014.626 4011.877 4Go9.101 4006.323 4003.533 4wo.713 3997.891
P(J)OBS.
4087.915
4090.975 4090.930 4090.872 4090.824 4090.764 4090.701 4090.633 4090.559 4090.482 4090.400 4090.313 4090.219 4090.126 4090.026 4089.917 4089.811 4089.691 4089.575 4089.452 4089.322 4089.IM 4089.047 4088.9O?f 4088.744 4088.592 4088.427 4088.261
4091.051
qmoas.
12C12CH* (looo”l’) - (ooco”oo)
12C12CH2
4179.598
4143.565 4145.883 4148.197 4150.520 4152.819 4155.106 4157.389 4159.648 4161.908 4164.167 4166.398 4168.631 4170.856 4173.052 4175.250
R(J,OBS.
4087.567 4085.033 4082.530
4102.657 4100.148 4097.641 4095.142 4092.609
4122.228 4119.808 4117.378 4114.956 4112.519 4110.062
4131.788 4129.421 4127.013
P(J)OBS.
4141.930
4139.034 4139.095 4139.164 4139.247 4139.322 4139.426 4139.537 4139.656 4139.774 4139.902 4140.036 4140.175 4140.329 4140.483 4140.645 4140.806 4140.975 4141.148 4141.330 4141.539
4138.938
4138.898
QWOSS.
(01co"31) - vmc0ooo)
W2C”
4113.833 4115.905 4117.948 4119.984 4122.011 4124.004 4125.993 4127.974 4129.956 4131.903
4109.664
4101.141 4103.301 4105.441
4092.428 4094.624 4096.813
4081.197 4083.473 4085.742 4087.970
R(J)OBS.
4020.200 4017.605 4014.977 4012.335 4009.695 4007.043
4040.599 4038.100 4035.581 4093.042 4030.487 4027.935
4050.496 4048.041 4045.571
4067.305 4064.935 4062.564 4060.181 4057.774 4055.368
P(J)OBS.
4078.704 4078.652 4078.603 4078.555 4078.496 4078.429 4078.39x 4078.302 4078.214t 4078.148 4078.060 4077.992t 4077.886 4077.784+ 4077.690 4077.566+ 4077.476
Q(J)OSS.
(looool') - (OE0ooOO)
;: 33 34 35 36 37
G 29 30
::
:; 20 21 22 23 24
2 7 a 9 10 11 12 13 14 15 16 17
2 3 4
0 1
.I
NOTES
602
(1”“11,1)*-(0001’0”) d-d
1 2 3 4 5 6 7 8 9 1” 11 12 13 14
4081.812 4084.128 4086.454 4088.144 4091.027 4093.272 4095.527 4097.741 4099.96” 4102.173 4104.348 4106.525 4108.685 4110.818
4067.615 4065.19” 4062.77” 4060.326 4057.862 4055.368 4052.901 4050.401 4047.886 4045.354 4042.805 4040.248 4037.682 4035.103 4032.505 4029.887 4027.258 4024.618 4021.964 4”,9.,“6 4016.643 4013.94” 4”,1.241 4005.804 4003.064 4”““. 285
+ Blended
4080.332 4082.681 4084.969 4087.256
4077.038 4076.971 4076.882 4076.843 4076.797 4076.737 4076.683 4076.621 4076.553 4076.48” 4076.411 4076.332 4076.25” 4076.17” 4076.081 4075.984 4075.884 4075.791
(1”“1111)“-(“0”11”“)
dtd
4091 .*a0 ‘“94.041 4096.279 4098.497 4100.691 4102.892
cc-c
4068.537 4061.8”” 4061.732 4061.653 4061.547t 4061.453 4061.333 1061.197 4061.05” 4060.875 4060.69” 4060.489 4060.267 4060.032 4059.768
4063.724 4061.29” 4058.852 4056.391 4053.929 4051.433 4048.927
4059.174 4058.852 4058.514 4058.15”
4075.567
lines
4073.248 4070.902 ‘“68.537 4066.167 4063.794 4061.406 4059.018 ‘“56.642 4054.256 4051.857 4049.45‘3 4047.074 4044.694 4042.299 4039.907 4037.526 4035.103
+ Blended
(1”“1~1’)“- (“o”11”“3 dtc
lines
4017.992 4080.332 4082.681 4080.149 4080.075 4079.968 4079.846 4079.73, 4079.604 4079.453 4079.314
4087.334 4091.959 4094.227+ 4096.556 4098.842 4101.123
4 5 6 7 8 9 1” 11 12 13 14 15 16 17 18 19 2” 21 22 23
NOTES
-
603
FIG. 1. Effects of perturbations in iZCxH~ bands. Erratum: The labeling of the band ~1 + (~4 + Y#’ Y,,’ is erroneously given as Y~(Y( + Y# - ~4~in the left half of the figure.
The main conclusions reached in the present work are summarized below. The molecular constants determined are consistent with the information obtained from the experimental data for nearly thirty other bands of acetylene studied in this laboratory. The spectral resolution available at 2.4 p allowed the observation of Q branch structures in addition to the R and P branches and therefore, we could study the molecular constants in greater detail. This was not possible in the case of the emission work (1). Second, the observational effect of perturbations in states where the 214= 1 and 210= 1 levels are simultaneously excited are similar to those observed earlier (5, 6). These effects are clearly evident from the reproduction shown in Fig. 1 where the appropriate combination relations are plotted. Finally, we find that the gj:, constant is correct as in Refs. _ 3 and 3 and the difference from the determination in Ref. 1 is probably due to the way in which this constant has been defined in that work. ACKNOWLEDGMENTS The financial support extended by the C. N. R., Italy is gratefully acknowledged. One of us (K. N. R.) would like to express his thanks for the part support extended this research by the National Science Foundation. REFERENCES 1. Y. DELAVAL, J. CARTIGNY, ANDJ. LECOMTE, Volume Jubilaire Louis d’Or, Memoire Hors Serie de la SociCt6 Royale des Sciences de Liege, Belgium, pp. 65-74 (1971). 2. K. F. PALMER, M. E. MICKELSON, AND K. NARAHARIRAO, J. Mol. Spectrosc. 44, 131 (1972); see K. F. PALMER, Ph.D. dissertation, The Ohio State University, 1972 for more details. 3. J. PLfVA, J. Mol. Speclrosc. 44, 165 (1972). 4. T. A. WIGGINS, E. K. PLYLER, ANDE. D. TIDWELL, J. Opt. Sot. Amer. 51, 1219 (1961). 5. K. F. PALMER, S. GHERSETTI, ANDK. NARAHARIRAO, J. Mol. Spectrosc. 30, 146 (1969). 6. A. BALDACCI,S. GHERSETTI, ANDK. NARAHARIRAO, J. Mol. Spectrosc. 34, 3.58 (1970). Ueparlment of Organic Chemistry Universily of Venke CaUe Larga S. Marta 2137 verresti (Italy) I)eparlment cf Physics The Ohio State University Colmbus, Ohio 43210 Received: June 1, 1973
AGOSTINO BALDACCI SERGIO GHERSETTI
K. NARAHARI RACI