FTIR Spectroscopy of the 4 bands of 14 NO 3 and 15 NO 3 (Okayama Univ., Hiroshima City Univ.) R....

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FTIR Spectroscopy of t he 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

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.

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.

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

Page 3: 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.

Experimental setup

Liq. He Si bolometer

0.006 cm-1 resolution

Effective path length :48-m

Page 4: 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.

Detector part – Silicon BolometerDewar temperature 4.2 K to 1.7 K

Page 5: 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.

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)

Page 6: 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.

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)

Page 7: 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.

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.

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.

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

Page 10: 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.

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

Page 11: 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.

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)

Page 12: 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.

Inertial defect of planar symmetric top molecule

harmonic frequencies and 3

Jagod and Oka (1990, JMS)

Check of vibrational assignment

Page 13: 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.

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

Page 14: 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.

     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 %

Page 15: 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.

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

Page 16: 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.

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

Page 17: 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.

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