High resolution absorption spectrum of nitric oxide (NO) in the region of the first ionization limit
Abstract
The absorption spectrum of cold NO gas has been photographed at high resolution between 1400 and 1250 Å for two isotopic species. Resolved bands of the Rydberg series converging to vibrational levels of the 1Σ+ ground state of NO+ are studied. They include nf–X bands up to n = 15 and ns–X bands up to n = 11, all of which show sharp rotational structure. The higher members of the np–X series are generally very diffuse with only npσ being sufficiently sharp to show broadened rotational lines. Also mostly diffuse are the ndδ–X bands. The bands ndσ, π–X are not observed. The rapidly (n−3) narrowing structure of the nf complexes is discussed and the ionization energy 
accurately determined by extrapolation of selected rotational lines. Interactions between Rydberg states are numerous, s ~ d mixing produces a strong effect above n = 6 when (n + 1)s levels fuse with nl levels into 'supercomplexes'. Matrix elements are given for observed 8f ~ 9s and 6f ~ 6dδ interactions.Valence levels are not observed above the ionization energy, except for the repulsive state A′2Σ+ arising from the first dissociation limit and seemingly assuming Rydberg character at molecular internuclear distance. Observed anomalies are qualitatively discussed.
accurately determined by extrapolation of selected rotational lines. Interactions between Rydberg states are numerous, s ~ d mixing produces a strong effect above n = 6 when (n + 1)s levels fuse with nl levels into 'supercomplexes'. Matrix elements are given for observed 8f ~ 9s and 6f ~ 6dδ interactions.Valence levels are not observed above the ionization energy, except for the repulsive state A′2Σ+ arising from the first dissociation limit and seemingly assuming Rydberg character at molecular internuclear distance. Observed anomalies are qualitatively discussed.Résumé
Le spectre d'absorption du gaz NO froid a été photographié à haute résolution entre 1400 et 1250 Å pour deux espèces isotopiques. Les bandes résolues des séries de Rydberg, convergentes vers des niveaux vibrationels de l'état fondamental de NO+, sont étudiées. Elles comprennent les bandes nf–X jusqu'à n = 15 et ns–X y compris n = 11. Toutes ces bandes montrent une structure rotationelle bien nette. Les membres plus élevés de la série np–X sont généralement très diffuses, seulement npσ–X se montre parfois avec des raies rotationelles séparées mais élargies. Aussi la plupart des bandes ndδ–X est diffuse, tandis que ndσ, π–X n'est pas observée. La structure des complexes nf, se rétrécissant vite (n−3) avec n, est discutée, et l'énergie d'ionisation 
est déterminée exactement par extrapolation de certaines raies rotationelles. Les interactions entre états Rydberg sont nombreuses. Un fort effet est produit par mélange s ~ d, dès qu'au dessus de n = 6 les niveaux (n + 1)s fusionnent avec n en 'supercomplexes'. Des éléments de matrice sont donnés pour des interactions observées 8f ~ 9s et 6f ~ 6dδ.Aucun niveau de valence n'est observé au dessus de l'énergie d'ionisation à l'exception de l'état répulsive A′2Σ+ provenant de la première limite de dissociation. Cet état parâit prendre à des distances entrenucléaires moléculaires un caractère Rydberg. Les anomalies observées sont discutées qualitativement.
est déterminée exactement par extrapolation de certaines raies rotationelles. Les interactions entre états Rydberg sont nombreuses. Un fort effet est produit par mélange s ~ d, dès qu'au dessus de n = 6 les niveaux (n + 1)s fusionnent avec n en 'supercomplexes'. Des éléments de matrice sont donnés pour des interactions observées 8f ~ 9s et 6f ~ 6dδ.Aucun niveau de valence n'est observé au dessus de l'énergie d'ionisation à l'exception de l'état répulsive A′2Σ+ provenant de la première limite de dissociation. Cet état parâit prendre à des distances entrenucléaires moléculaires un caractère Rydberg. Les anomalies observées sont discutées qualitativement.Get full access to this article
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Published In
Canadian Journal of Physics
Volume 54 • Number 20 • October 1976
Pages: 2074 - 2092
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Version of record online: 11 February 2011
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E. Miescher. 1976. High resolution absorption spectrum of nitric oxide (NO) in the region of the first ionization limit. Canadian Journal of Physics.
54(20): 2074-2092. https://doi.org/10.1139/p76-246
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p
Rydberg complex of a molecular ion: MgAr+. II. Global analysis of the A+ 2Π and B+ 2Σ+ (3pσ,π) states
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3. Ultrafast population transfer to excited valence levels of a molecule driven by x-ray pulses
4. Far-infrared amplified emission from the v= 1 autoionizing Rydberg states of NO
5. Far infrared stimulated emission from the
ns
and
nf
Rydberg states of NO
6. Time-slice velocity-map ion imaging studies of the photodissociation of NO in the vacuum ultraviolet region
7. Time–energy mapping of photoelectron angular distribution: application to photoionization stereodynamics of nitric oxide
8. High‐resolution Photoelectron Spectroscopy
9. A theoretical study of the rotational structure of the ϵ(0,0) band of NO
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11. Structure and Dynamics of High Rydberg States Studied by High-Resolution Spectroscopy and Multichannel Quantum Defect Theory
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13. Rotational-state-selective field ionization of molecular Rydberg states
14. Photodissociation of the
δ
(0,0) and
δ
(1,0) bands of nitric oxide in the stratosphere and the mesosphere: A molecular‐adapted quantum defect orbital calculation of photolysis rate constants
15. Observation of the Stark effect in υ
+
= 0 Rydberg states of NO with a matrix-diagonalization analysis
16. Far infrared stimulated emission from the 8s and 8f Rydberg states of NO
17. Theoretical study of the rotational structure of the γ(0, 0) band of NO. Molecular quantum defect orbital (MQDO) calculations of Einstein absorption coefficients and line-integrated rotational cross sections
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20. Radiative lifetimes for the A
2
Σ
+
(
v
′ = 0–7) and D
2
Σ
+
(
v
′ = 0–5) Rydberg states of NO
21. Photoionization studies of the atmospherically important species N and OH at the Elettra synchrotron radiation source
22. Optical-optical double resonance photoionization spectroscopy of nf Rydberg states of nitric oxide
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24. Photodissociation Dynamics
25. Terms Neglected in the Born-Oppenheimer Approximation
26. The Heterolytic Dissociation of Neutral and Protonated Nitrous Acid
27. Control of vibrational ionization branching through feedback-optimized tailored femtosecond laser pulses
28. High-resolution laser absorption spectroscopy in the extreme ultraviolet
29. Intensities of Vibronic Transitions for the Main Bands Observed in the Electronic Spectrum of Atmospherically Relevant Nitric Oxide
30. References
31. Stabilization of predissociating nitric oxide Rydberg molecules using microwave and radio-frequency fields
32. Rydberg-state-resolved zero-kinetic-energy photoelectron spectroscopy
33. Ionization-detected opticaloptical double resonance spectroscopic studies of moderate energy Rydberg states of calcium monofluoride
34. Partial-Wave Decomposition of the Ionization Continuum Accessed by Vibrational Autoionization of the NO
14s
(
ν=1
,
N=20
,
NR+=20
) Level
35. Rotational-resolved pulsed field ionization photoelectron study of NO+(X 1Σ+,v+=0–32) in the energy range of 9.24–16.80 eV
36. Lifetime control in Rydberg states using fast switching DC electric fields
37. Dynamics of Rydberg states of nitric oxide probed by two-color resonant four-wave mixing spectroscopy
38. Vibrational autoionization and predissociation in high Rydberg states of nitric oxide
39. On the role of ions in pulsed field ionization zero–kinetic–energy photoelectron spectroscopy
40. Rotationally resolved photoelectron spectra from vibrational autoionization of NO Rydberg levels
41. High Rydberg states of the NO molecule studied by two-color four-wave mixing spectroscopy
42. High n Rydberg spectroscopy of benzene: Dynamics, ionization energy and rotational constants of the cation
43. Chapter 6. Gas-phase molecular spectroscopy
44. Intramolecular coupling between non-penetrating high molecular Rydberg states
45. R
-matrix calculation of the bound and continuum states of the - system
46. The dynamics of predissociating high Rydberg states of NO
47. Rotationally resolved high (n > 100) Rydberg states of benzene
48. Extensive Electron-Nuclear Angular Momentum Exchange in Vibrational Autoionization of
np
and
nf
Rydberg States of NO
49. Core Hole Double-Excitation and Atomiclike Auger Decay in
N2
50. Three-color triple resonance spectroscopy of highly excited
ng
Rydberg states of NO: Decay dynamics of high-
l
Rydberg states
51. Two-photon ionization and dissociation of ethyl iodide
52. The dynamics of high autoionizing Rydberg states of Ar
53. Lifetimes of Rydberg states in zero-electron-kinetic-energy experiments. I. Electric field induced and collisional enhancement of NO predissociation lifetimes
54. Photoelectron Angular Distributions of Rotationally Selected NO Rydberg States
55. Photoionization and photodissociation of nitric oxide in the range 9–35 eV
56. Basic principles of ZEKE spectroscopy. Optimized resolution and accurate ionization energy
57. Time-resolved multiphoton ionization study of the 102 nm state of NO
58. Line shapes and forced autoionization of the 8
s
and 9
s
,
v
=1 Rydberg states of NO
59. The
f
Rydberg series in the absorption spectrum of N2
60. Rotational analysis of
n
=4–7 Rydberg states of CO observed by ion-dip spectroscopy
61. Zero-kinetic-energy photoelectron spectrum of carbon dioxide
62. Single-photon threshold photoionization of NO
63. Absolute optical oscillator strengths for the photoabsorption of nitric oxide (5–30 eV) at high resolution
64. Observation of NO
B
2Π(
v
=3)←
X
2Π(
v
=0) absorptions with 1+1 multiphoton ionization: Precision line position measurements and parity assignment of the
B
2Π state
65. Measurement of circular dichroism in rotationally resolved photoelectron angular distributions following the photoionization of NO
A
2Σ+
66. Rotational analysis of
v
=1 level of
n
=8∼10 Rydberg states of CO by triple resonant multiphoton spectroscopy
67. Rotational state dependence of decay dynamics in the superexcited 7
f
Rydberg state (υ=1) of NO
68. 193 nm photodissociation dynamics of nitromethane
69. High-resolution zero kinetic energy electron spectroscopy of ammonia
70. Zero kinetic energy electron spectroscopy of molecules: Rotational symmetry selection rules and intensities
71. Detection of nitrogen atoms produced by predissociation of superexcited Rydberg states of NO
72. CEPA calculations on highly excited states:
2
Sigma
+
Rydberg series of NO
73. On the 3d Rydberg states of the NO molecule
74. s and d Rydberg complexes of NO probed by double-resonance multiphoton ionisation in the region
n
* = 5 to
n
* = 25; multichannel quantum defect analysis. Part II
75. The emission spectrum of helium hydride. III. Bands near 5200, 5300, and 6000 Å
76. Two-photon spectroscopy of Rydberg states of molecular oxygen
77. Interaction of auto-decayed states in molecule photodissociation processes
78. N(2
D
) production from predissociation of
ns
and
nd
Rydberg levels in NO
79. Vacuum ultraviolet–visible double resonance spectroscopy of NO. Observation of the high excited
ns
and
nd
Rydberg series
80. Two-photon spectroscopy of Rydberg states of NO
81. Optical–optical double resonance studies of rotational autoionization of NO
82. The ionization energy of nitric oxide
83. High resolution laser spectroscopy of NO: The
A
,
v
=1 state and a series of
nf
,
v
=1 Rydberg states
84. Near-threshold associative ionisation reactions of atoms
85. Analysis of the 4
f
,
v
=3 state of NO
86. Rotationally resolved double resonance spectra of NO Rydberg states near the first ionization limit
87. High-resolution zero-kinetic-energy photoelectron spectroscopy of nitric oxide
88. A unified treatment of 2Π–2Π Rydberg–valence state interactions in NO
89. Fourier transform emission spectroscopy with supersonic jets
90. s
and
d
Rydberg series of NO probed by double resonance multiphoton ionization
91. Vacuum ultraviolet laser spectroscopy: Radiative lifetimes of interacting 2Δ states of NO
92. Molecular dynamic photoelectron spectroscopy using resonant multiphoton ionization for photophysics and photochemistry
93. Wavelength dependent photoelectron spectra of rotationally resolved autoionizing levels of nitric oxide
94. The photodissociation of molecules near the ionisation threshold
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96. The 4
f
states of He
2
: A new spectrum of He
2
in the near infrared
97. Predissociation
98. Terms Neglected in the Born—Oppenheimer Approximation
99. High-resolution one-photon ionization spectrum of no using third-harmonic generation
100. Two-color multiphoton ionization and fluorescence dip spectra of NO in a supersonic free jet. Highly excited ns, np, nf Rydberg states
101. Rydberg states and quantum defects of the NO molecule
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104. Molecular Applications of Quantum Defect Theory
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106. Two-color excitation of NO in a supersonic free jet. Autoionization of high rydberg states
107. Theoretical study of competing photoionization and photodissociation processes in the NO molecule
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110. Molecular Beam Photoionization Studies of Molecules and Clusters
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112. A theoretical analysis of the four-photon ionization spectrum of the nitric oxide molecule
113. Molecular beam photoionization study of CO, N2, and NO dimers and clusters
114. Near infrared transitions between Rydberg states of nitric oxide
115. Higher resolution photoionization study of NO near the threshold
116. The chemistry of excited NO
+
in an aurora
117. Potential energy curves for NO+
118. Ionization energy values for the transitions NO+,X1Σ+(v′ = 0—34) ← NO, X2 φ (v″, = 0) and molecular constan
119. Autoionization structure of nitric oxide (NO) at the first ionization limit
120. Pressure induced configuration demixing in the electronic spectrum of NO
121. The I2Σ+ state of the NO molecule
122. Rydberg series of NO converging to the ionic states , , and
123. Rovibronic interactions in the photoabsorption spectrum of molecular hydrogen and deuterium: An application of multichannel quantum defect methods
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