FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R....
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Transcript of FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R....
![Page 1: FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R. Fujimori, N. Shimizu, J. Tang, K. Kawaguchi, T. Ishiwata.](https://reader030.fdocuments.in/reader030/viewer/2022032605/56649e7c5503460f94b7df75/html5/thumbnails/1.jpg)
FTIR Spectroscopy of the 4 bands of 14NO3 and 15NO3
(Okayama Univ., Hiroshima City Univ.)R. Fujimori, N. Shimizu, J. Tang,
K. Kawaguchi, T. Ishiwata
![Page 2: FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R. Fujimori, N. Shimizu, J. Tang, K. Kawaguchi, T. Ishiwata.](https://reader030.fdocuments.in/reader030/viewer/2022032605/56649e7c5503460f94b7df75/html5/thumbnails/2.jpg)
Infrared study of NO3
Present study ; first gas-phase spectroscopy of 4
Determination of C0 from K=3 Combination Difference
( selection rule K = ±1 for 4,
combined with other measurements)
Calculation of inertial defect
1 ; inactive2 ; Friedl and Sander(1987)3 ; very weak intensityOnly Matrix isolation observation ( Beckers, Willner, Jacox. 2009)
Four fundamental bands
Gr.K
K+1
K+2
K+3
4.
3+4.
K=3 CD
1492 1127
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Experimental setup
Liq. He Si bolometer
0.006 cm-1 resolution
Effective path length :48-m
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Detector part – Silicon BolometerDewar temperature 4.2 K to 1.7 K
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Monitoring of NO3 concentration by HeNe laser
Abs
orpt
ion
of
HeN
e La
ser
discharge On
discharge Off
10 % absorption
Absorption spectrum of the NO3 B-X band
HeNe
(3-m path length)
Sander, J. Phys. Chem. (1986)
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Observed spectrum of 14NO3 radical
355.8 355.9 356.0 356.1 356.2 356.3 356.4
0.00
0.05
0.10
(13,6)
(14,9)
(15,12)
(16,15)
pP(N,K)
abso
rban
ce
wavenumber (cm- 1)
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Analysis4 band 114 lines PP(N,K) K=5 ~ 29
K=3 ground state combination differences
4 (365), 3+4-4 (1127), 3+4 (1492)
4 combination differences
3+4-4 (1127), 3+4 (1492)
K=0 ground state combination differences
3+4 (1492) rQ(N+1,K) and rR(N,K)
pQ(N-1,K) and pP(N,K)
![Page 8: FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R. Fujimori, N. Shimizu, J. Tang, K. Kawaguchi, T. Ishiwata.](https://reader030.fdocuments.in/reader030/viewer/2022032605/56649e7c5503460f94b7df75/html5/thumbnails/8.jpg)
K = 12
365 cm-1 band
4
Combination differences for K=3 and 4
1492 cm-1
3 + 4
1127 cm-1
15
14
13 14
13
Gr K = 3 combination differences
4 combination
differences
3 hot band of 15NO3 was newly observed
![Page 9: FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R. Fujimori, N. Shimizu, J. Tang, K. Kawaguchi, T. Ishiwata.](https://reader030.fdocuments.in/reader030/viewer/2022032605/56649e7c5503460f94b7df75/html5/thumbnails/9.jpg)
Statistical weight in Analysis4 band 114 lines PP(N,K) K=5 ~ 29 Weight = 1 (accuracy 0.001 cm-1)K=3 ground state combination differences 4 (365), 3+4-4 (1127), 3+4 (1492) Weight = 1/34 combination differences 3+4-4 (1127), 3+4 (1492) Weight = 1/2K=0 ground state combination differences 3+4 (1492) Including diode laser data Weight = 1/2
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14NO3 and 15NO3 molecular constants(1)
(Ground state) 14NO3 15NO3
present previous present B 0.4585445(86) 0.4585485(63) 0.458613(14) C 0.2286679(57) [0.2292743] 0.2287127(89) DN ☓105 0.1092(13) 0.1113(12) 0.1090(25) DNK☓105 -0.2073(26) -0.2121(27) -0.2017(65) DK ☓105 0.1072(18) [0.1034] 0.0995(52) bb -0.01621(20) -0.01649(13) -0.01549(26) cc 0.00079(14) [0.0] [0.00079]
fit=0.0013 cm-1
DKx105(calc) 0.101 0.0977
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present previous present 0 365.48776(35) 365.48419(43) 360.20294(59)B 0.4592093(41) 0.4592222(60) 0.4592148(90)C 0.2282897(28) 0.2278233(40) 0.2283252(36)DN ☓105 0.0924(16) 0.1019(23) 0.0953(44)DNK☓105 -0.1643(41) -0.1953(58) -0.169(13)DK ☓105 0.0801(28) 0.0973(40) 0.0815(97)C -0.042984(14) -0.042063(15) 0.035723(23)N☓105 -0.470(21) -0.431(28) -0.48(13)K☓105 0.379(27) 0.382(36) 0.40(13)q4 0.013276(15) 0.013363(22) 0.013360(66)aeff -0.16581(44) -0.17016(36) -0.16606(50)bb -0.015376(36) -0.015766(36)-0.014498(53)cc 0.000761(26) [0.0] 0.000664(33)
(4 state) 14NO3 15NO3
14NO3 and 15NO3 molecular constants(2)
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Inertial defect of planar symmetric top molecule
harmonic frequencies and 3
Jagod and Oka (1990, JMS)
Check of vibrational assignment
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v1 v2 v3 v4 obs calc obs-calc
0 0 0 0 0.1967 0.1961 0.0005 0.3% 1 0 0 0 0.1968 0.1961 0.0007 0.4% 0 1 0 0 0.0665 0.0763 -0.0097 13 % 0 0 1 0 0.2436 0.2573 -0.0137 5 % 0 0 0 1 0.3936 0.3910 0.0026 2 0 0 1 0.4222 0.3910 0.0311 0 2 0 0 -0.0639 -0.0436 -0.0204 30%(max) 0 0 2 0 0.2900 0.3184 -0.0284 0 0 0 2 0.5894 0.5859 0.0035 0 0 0 2 0.5916 0.5859 0.0056 1 1 0 0 0.0798 0.0763 0.0035 1 0 1 0 0.2228 0.2573 -0.0345 1 0 0 1 0.4079 0.3910 0.0169 0 1 0 1 0.2619 0.2712 -0.0093 0 0 1 1 0.4278 0.4522 -0.0244
Inertial defect in BF3 (example, data Maki et al. JMS )
obs=Ic-2 Ib
amu Å2
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Obs. Calc. O-C Gr. 0.206 0.223 -0.017(0001) 0.434 0.437 -0.003(1001) 0.474 0.437 0.037(00031 1.091 0.864 0.227(0011) 0.367 0.487 0.120
3 + 4 = 0 (D3h )
1 (1050), 2 (762) 3 (1127), 4 (365)
In this calc, if 3 = 1492, 3 calc = 0.237Disagreement with observed
Inertial Defects (amu Å2) of NO3
1492 band 3 + 4 ≠ 0 not in D3h (Jahn-Tellar effect )
large p34 [splitting in K=1], aa-bb≠0
4
1+4
34
3+4
=Ic - 2Ib
8 %0.7 %8 %21 %24 %
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Relative infrared intensity
3+4(1492 band) = 1.00
band Obs. Calc. ( Stanton ) ν4 (365 cm-1) 0.59 0.26
3ν4 (1173) 0.03 0.06
ν1+ν4 (1413) 0.12 0.31
ν3+ν4 (1492) 1.00 1.00
ν3+2ν4(1927) 0.65 0.13 J. F. Stanton, Molecular Physics, 107.1059 (2009)
Agreement within factor 2 except for ν3+2ν4
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Summary
1. Measurement of the 4 band of NO3
Present 365.7871 cm-1
Matrix 365.6 cm-1
Isotope shift (14N - 15N) = 5.5851 cm-1
2. Determination of C0
0.2286321 (67) cm-1 14NO3
0.228674 (11) cm-1 15NO3
3. Calculations of Inertial defect
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v1 v2 v3 v4 obs calc obs-calc 0 0 0 0 0.1576 0.1585 -0.0008 0 1 0 0 0.3089 -1.0765 1.3855 0 0 1 0 0.1776 0.1732 0.0044 0 0 0 1 0.2245 0.9196 -0.6951 0 0 0 1 0.3782 0.9196 -0.5414 0 2 0 0 -0.0975 -2.3115 2.2141 0 0 2 0 0.1981 0.1880 0.0102 0 0 0 2 0.5424 1.6808 -1.1384 0 0 0 2 0.5445 1.6808 -1.1363 1 1 0 0 0.3317 -1.0765 1.4082 0 0 1 0 0.1827 0.1732 0.0095 1 0 0 1 0.2041 0.9196 -0.7156 0 1 0 1 0.2216 -0.3153 0.5370 0 0 1 1 0.2544 0.9344 -0.6800 0 0 0 0 0.1576 0.1585 -0.0008 0 0 0 3 0.3679 2.4420 -2.0741 0 1 0 2 0.4369 0.4458 -0.0090 0 2 0 1 0.5243 -1.5503 2.0746 0 1 1 0 0.2999 -1.0618 1.3616
Inertial defect in SO3 (example, data Maki et al. JMS )
obs=Ic-2 Ib
amu Å2