Absorption spectrum of the NO molecule. IX. The structure of the f complexes, the ionization potential of NO, and the quadrupole moment of NO+

1969 ◽  
Vol 47 (17) ◽  
pp. 1769-1787 ◽  
Author(s):  
Ch. Jungen ◽  
E. Miescher
Keyword(s):  
Nitric Oxide ◽  
Absorption Spectrum ◽  
Angular Momentum ◽  
High Resolution ◽  
Ionization Potential ◽  
Quadrupole Moment ◽  
Electron Spin ◽  
Rydberg Series ◽  
Molecular Core ◽  
Rydberg Electron

The 0–0 bands at 1474 Å and 1422 Å of the first two members of the nf–X2Π Rydberg series of NO have been observed under high resolution in the absorption spectrum of cold nitric oxide gas. They show an abnormal rotational structure which has been analyzed with the help of a computer program. The uncoupling of the angular momentum l = 3 of the f electron in the rotating molecule is discussed theoretically, including the effect of electron spin and interaction with the molecular core. The connection between the electronic energies TΛ of the f complex in the nonrotating molecule and the electronic energies [Formula: see text] in the rapidly rotating molecule is given. From the analysis a precise value of the ionization potential of NO is obtained, viz. T∞ = 9.2639 ± 0.0006 eV, and the quadrupole moment of the molecular ion NO+ is determined to be Qzz = +(0.79 ± 0.06) 10−26 e.s.u. cm2. The "atomic" and the "molecular" properties of a highly excited molecular Rydberg electron are discussed.

Autoionization resonances in the Eu I absorption spectrum and a new determination of the ionization potential

1975 ◽  
Vol 342 (1628) ◽  
pp. 149-156 ◽  
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Ionization Potential ◽  
Wavelength Region ◽  
Rydberg Series ◽  
A Value ◽  
Ionization Limit ◽  
The Eu

The absorption spectrum of europium has been studied at high resolution in the wavelength region between 2200 and 2100 Å. Two Rydberg series were found converging towards the 9 S 4 and 7 S 3 levels of the configuration 4f 7 6s in Eu II. The first series is perturbed near the series limit and the second shows strong autoionization features. A value of 45734.9 ± 0.2 cm -1 is deduced for the first ionization limit.

Absorption spectrum of the NO molecule. VIII. The heterogeneous (2Σ–2Π) interactions between excited states

1968 ◽  
Vol 46 (8) ◽  
pp. 987-1003 ◽  
Author(s):  
Ch. Jungen ◽  
E. Miescher
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Excited States ◽  
Rydberg State ◽  
Vacuum Ultraviolet ◽  
Principal Quantum Number ◽  
Rydberg States ◽  
Infrared Emission ◽  
Strong Interactions ◽  
Rydberg Series

Heterogeneous perturbations 2E+ ~ 2Π of largely different magnitudes are observed with high resolution in the vacuum-ultraviolet absorption and in the infrared emission spectrum of the NO molecule. The rotational interactions between 2Σ+ Rydberg states and levels of the B2Π non-Rydberg state are shown to be "configurationally forbidden", but produced by the configuration interaction between the non-Rydberg levels and 2Π Rydberg states. The latter together with the 2Σ+ Rydberg states form p complexes. In this way the interactions display the l uncoupling in the complexes; they can be evaluated theoretically and can be analyzed fully. The cases of the strong interactions D2Σ+(v = 3) ~ B2Π(v = 16)and D2Σ+(v = 5) ~ B2Π(v = 21) and of the weaker D2Σ+(v = 1) ~ B2Π(v = 11), all three observed as perturbations in ε bands crossing 3 bands, are discussed in detail. It is further shown that perturbations between γ bands and β bands as well as perturbations between analogous bands of higher principal quantum number are absent, and thus the assignment of the A2Σ+ and E2Σ+ states to the s Rydberg series is confirmed.

ON THE ABSORPTION SPECTRUM OF H2O AND D2O IN THE VACUUM ULTRAVIOLET

1963 ◽  
Vol 41 (2) ◽  
pp. 209-219 ◽  
Author(s):  
J. W. C. Johns
Keyword(s):  
Absorption Spectrum ◽  
Water Vapor ◽  
High Resolution ◽  
Heavy Water ◽  
Vacuum Ultraviolet ◽  
Rydberg Series ◽  
Accuracy Of Measurement ◽  
Concave Grating

The spectra of normal and heavy water vapor have been observed under high resolution in the region 1220–1240 Å. One band of H2O and two bands of D2O have been measured and analyzed. The spectra were taken in the ninth order of a 35-ft concave-grating spectrograph and the accuracy of measurement of the sharper lines is estimated to be about ± 0.005 Å. The results of the analyses are summarized below.[Formula: see text]These bands have been assigned as belonging to the first member of one of the two np Rydberg series.

Rydberg series and autoionization resonances in the Y I absorption spectrum

1973 ◽  
Vol 333 (1592) ◽  
pp. 17-24 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Ionization Potential ◽  
Excited States ◽  
Spectral Range ◽  
Ground State ◽  
Rydberg Series ◽  
A Value ◽  
Doublet Ground State ◽  
Ionization Limit ◽  
First Ionization Potential

The absorption spectrum of yttrium vapour has been photographed in the spectral range 1650 to 2250 À, with a 10 m spectrograph. Series of autoionization resonances, which converge on excited states of the Y + ion have been identified, as combinations with the doublet ground-state of Y I , 5s 2 4d 2 D 3/2 , 5/2 . Although the lines of these series show broadened and often asymmetrical profiles, the lines are sufficiently well defined to fix a value for the first ionization potential of Y I , which differs from the previously accepted value by approximately 2500 cm -1 . In addition, approximately 400 new Y I lines, which involve excited levels below the first ionization limit of Y I , namely 4s 2 1 S o , have been found. The majority of these are unclassifiable at present but, the value for the first ionization-potential being known from the resonances above-mentioned, two series of the character 5s 2 4d 2 D 3/2 , 5/2 -5s 2 nf 2 F o have been identified. In addition to the identifications of series, 152 new lines below the 5s 2 1 S o limit identify 76 new levels of Y I , of odd parity.

High resolution absorption spectrum of nitric oxide (NO) in the region of the first ionization limit

1976 ◽  
Vol 54 (20) ◽  
pp. 2074-2092 ◽  
Author(s):  
E. Miescher
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Ionization Energy ◽  
Dissociation Limit ◽  
Matrix Elements ◽  
Rydberg Series ◽  
Isotopic Species ◽  
Vibrational Levels ◽  
Energy Formula ◽  
Ionization Limit

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 [Formula: see text] 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.

Absorption spectrum in the vacuum ultraviolet and visible emission spectrum of the NO molecule. The 4d complex

1969 ◽  
Vol 47 (8) ◽  
pp. 881-891 ◽  
Author(s):  
R. Suter
Keyword(s):  
Nitric Oxide ◽  
Absorption Spectrum ◽  
Emission Spectrum ◽  
Vacuum Ultraviolet ◽  
Visible Emission ◽  
Resolving Power ◽  
Weak Band ◽  
Oxide Molecule ◽  
Rydberg Electron

The structure of the 4d Rydberg term complex of the nitric oxide molecule has been studied by rotational analyses of the following bands photographed with spectrographs of high resolving power: (i) the weak band 4d–X2Π observed at 1470 Å in the absorption spectrum, (ii) the group 4d–3p of Rydberg–Rydberg bands observed as 4d–C2Π (6400 Å) and 4d–D2Σ+ (6800 Å) bands in the emission spectrum of a discharge. A type of l uncoupling of the Rydberg electron of the molecule is found very similar to the case already known for the 3d complex of NO. Constants characterizing the d complexes are calculated, and a comparison of the 3d and 4d complex is made.

High resolution absorption studies of the b1Πu ← X1Σg+ system of nitrogen

1969 ◽  
Vol 47 (5) ◽  
pp. 563-589 ◽  
Author(s):  
P. K. Carroll ◽  
C. P. Collins
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Triplet State ◽  
Rotational Structure ◽  
Dissociation Limit ◽  
Rydberg Series ◽  
Absorption Studies ◽  
Vibrational Levels ◽  
Single Transition ◽  
Made In

New high resolution studies of the absorption spectrum of N2 have been made in the region 1015–795 Å. Analyses are given of 25 non-Rydberg bands of the type 1Πu–X1Σg+. It is shown that all of these bands, which include the i, j, b, l, m, p, and q groups of Worley, together with several new bands not previously observed, can be assigned to a single transition the upper state of which is called b1Πu. The pronounced irregularities in the vibrational and rotational structure of the b state are attributed to a homogeneous interaction with the first member (n = 3) of the ---(3σg) npπu, 1Πu Rydberg series. This perturbation is discussed in the accompanying paper by Dressier who recognized its importance in the interpretation of the spectrum. Diffuseness in the rotational lines of several bands at lower ν was observed and is attributed to predissociation by a triplet state, probably the C′ 3Πu state which goes to the 4S + 2D dissociation limit. Three levels of the b state show measurable Λ-type doubling which can be interpreted as caused by interaction with vibrational levels of the first member (n = 4) of the --(3σg) npσu, 1Σu+ Rydberg series. The assignment of 28 non-Rydberg 1Σu+ levels, including the b′, g, f, r, s, and t "states", to a single 1Σu+ state which is called b′, is also briefly discussed.

Rydberg series and autoionization resonances in the Sc I absorption spectrum

1973 ◽  
Vol 333 (1592) ◽  
pp. 1-16 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Ionization Potential ◽  
Excited States ◽  
Spectral Range ◽  
Ground State ◽  
Rydberg Series ◽  
Doublet Ground State

The absorption spectrum of scandium vapour has been photographed in the spectral range 1200 to 3200 A, with 3 and 10 m spectrographs. Six long Rydberg series and two shorter ones have been identified, as combinations with the doublet ground -state of Sc I, 4s 2 3d 2 D3/ 2 , 5/2 . The series all converge on excited states of Sc n and nearly all their members lie in the continua beyond the 3d4s 3 D ground-levels of the ion, consequently showing a variety of autoionization profiles. The series yield a reliable value for the ionization potential of Sc I, which differs by only 2 cm -1 from an earlier estimate. The addition to the series, approximately 800 new lines of Sc I have been found. The majority of these are unclassifiable at present, and are not reported, but 236 of the lines, which locate 118 new odd levels of Sc I, are listed. Also, some major autoionization-broadened features, though not definitely classifiable, are described.

Electronic spectrum of the BF molecule

1970 ◽  
Vol 48 (4) ◽  
pp. 432-452 ◽  
Author(s):  
R. B. Caton ◽  
A. E. Douglas
Keyword(s):  
High Resolution ◽  
Emission Spectrum ◽  
Ionization Potential ◽  
Electronic Spectrum ◽  
Excited States ◽  
Electronic Absorption ◽  
Rydberg States ◽  
Electronic States ◽  
Rydberg Series ◽  
Absorption And Emission

The electronic absorption and emission spectrum of BF has been photographed at high resolution from 900 to 11 000 Å. In this work, many new electronic states have been found and corrections have been made to earlier work. The ionization potential has been determined to be between 89 635 and 89 680 cm−1, with the most probable value being 89 650 cm−1. Tables of the vibrational and rotational constants of all the known states of BF are presented. All but two of the excited states of BF have been classified as Rydberg states and have been assigned to Rydberg series. The interactions between the various Rydberg states are discussed.

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