Vacuum ultraviolet spectrum of the iodine molecule

1970 ◽  
Vol 48 (9) ◽  
pp. 1055-1079 ◽  
Author(s):  
Putcha Venkateswarlu

The absorption spectrum of iodine has been photographed in the higher orders of a 10.7 m concave grating spectrograph in the region 1950–1200 Å. A number of band systems has been obtained, most of which correspond to Rydberg transitions. The limit of the Rydberg series leading to the 2Π3/2g state of the molecular ion has been recorded and the corresponding ionization potential is found to be 75 814 ± 10 cm−1. Five series have been found which terminate at this common limit. They represent transitions from the ground state to [σg2πu4Πg32Π3/2g]np σu Π1u, [σg2πu4πg32Π3/2g]np πu Σ+ (0u+), [σg2πu4πg32Π3/2g]nf σu Π1u, [σg2πu4πg32Π3/2g]nf πu, Σ+(0u+), and [σg2πu4πg32Π3/2g]nf δu Π1u states respectively, where n takes the running values 6, 7, 8, … etc. for the first three series and 4, 5, 6, … etc. for the last two series. The series limit of the bands corresponding to the molecules with ν″ = 1 has been found to be at 75 600 ± 10 cm−1. The first few members of similar series corresponding to transitions to different states involving the common [σg2πu4πg32Π1/2g] core have been identified and the ionization limit of these series is estimated to be at 80 895 ± 50 cm−1. Some of the remaining band systems obtained have been found to be very likely due to transitions to the Rydberg states involving molecular ion cores like [σg2πu 3πg42Π3/2u], [σg2πu3πg42Π1/2u], and [σg2πu4πg2σu2Σu+]. Three of the observed band systems do not appear to involve Rydberg states and their upper levels are very likely the 1Π(1u), 3Π(1u), and 3Π(0u+) states arising from the configuration σgπu3πg4σu2. The positions of these levels are at 64 956, 62 844, and 61 847 cm−1, the corresponding vibrational frequencies being 145, 144, and 109 cm−1 respectively.

1969 ◽  
Vol 47 (22) ◽  
pp. 2525-2538 ◽  
Author(s):  
Putcha Venkateswarlu

The absorption spectrum of bromine has been photographed in the first and higher orders of a 10.7-m. concave vacuum grating spectrograph in the region 1700–1170 Å.A number of band systems have been obtained in the region 1510–1170 Å, most of which correspond to Rydberg transitions. In addition, an extensive band system with closely-spaced bands degraded to longer wavelengths has been recorded in the region 1700–1500 Å. Among the Rydberg systems, five series have been found to converge to 85 165 ± 80 cm−1 which represents the ionization potential of the molecule leading to the 2Π3/2g state of the molecular ion. They arise due to transitions from the ground state to [σg2πu4πg32Π3/2g]npσu, [σg2πu4πg32Π3/2g]npπu, [σg2πu4πg32Π3/2g]nfσu, [σg2πu4πg32Π3/2g]nfπu, and [σg2πu4πg32Π3/2g]nfδu configurations where n takes the running values 5, 6, 7, … etc. The first few members of four similar series corresponding to the transitions to the states involving the [σg2πu4πg32Π1/2g] core have been identified and the ionization limit of these series is estimated to be at 88 306 ± 80 cm−1. Two of the remaining band systems have been found to be very likely due to transitions to the Rydberg states with the configurations [σg2πu3πg42Π3/2u]5sσg and [σg2πu3πg42Π1/2u]5sσg, respectively. Three of the observed systems which do not involve Rydberg states appear to have for their upper levels the 1Πu(1u), 3Π(1u), and 3Π(0u+) states arising from the configuration σgπu3πg4σu2.


1975 ◽  
Vol 53 (8) ◽  
pp. 812-824 ◽  
Author(s):  
Putcha Venkateswarlu

The absorption spectrum of iodine chloride has been photographed in the high orders of a 10.7 m concave grating spectrograph in the region 1900–1220 Å. A number of band systems which correspond to Rydberg transitions have been obtained. In addition an extensive band system with closely spaced bands degraded to longer wavelengths has been observed in the region 1660–1580 Å. Among the Rydberg systems, 12 series have been found to converge to 81 362 ± 80 cm−1 which very likely represents the ionization potential of the molecule leading to the 2Π3/2 state of the molecular ion. They are due to transitions from the ground state to states arising from the configurations (σ2π4π32Π3/2)ns σ, (2Π3/2)np σ, (2Π3/2)np π, (2Π3/2)nd σ, (2Π3/2)nd π, (2Π3/2)nd δ, (2Π3/2)nf σ, (2Π3/2)nf π, and (2Π3/2)nf δ where n takes the running values 6, 7, 8, … for the first three configurations, 5, 6, 7, … for the next three configurations, and 4, 5, 6, … for the last three configurations. The first few numbers of 11 similar series corresponding to the transitions to the states involving the (σ2π4π32Π1/2) core have been identified and the ionization of these series is estimated to be at 85 996 ± 80 cm−1.


1987 ◽  
Vol 7 (2-4) ◽  
pp. 129-139 ◽  
Author(s):  
Toshiaki Munakata ◽  
Tadahiko Mizukuki ◽  
Akira Misu ◽  
Motowo Tsukakoshi ◽  
Takahiro Kasuya

The photoionization spectrum of HBr around the first ionization limit was measured at resolution of up to 5 x 10−4 nm. The ionizing vacuum ultraviolet radiation was generated by frequency tripling of the second harmonic output of a dye laser. Three sets of Rydberg series, each converging to the ground state (2Π3/2) of HBr+, were observed on the longer wavelength side of the ionization limit. By extrapolation of the Rydberg series, the ionization potential of HBr was determined to be 11.666 ± 0.001 eV.


1968 ◽  
Vol 46 (8) ◽  
pp. 987-1003 ◽  
Author(s):  
Ch. Jungen ◽  
E. Miescher

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.


1963 ◽  
Vol 41 (2) ◽  
pp. 209-219 ◽  
Author(s):  
J. W. C. Johns

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.


1972 ◽  
Vol 14 ◽  
pp. 531-531
Author(s):  
G. Mehlman-Balloffet ◽  
J. M. Esteva

AbstractAbsorption spectra of light elements were observed in the vacuum ultraviolet with an original technique described in an earlier paper (Mehlman-Balloffet and Esteva, 1969). The method utilizes a two-vacuum spark mounting: one of the sparks is emitting the continuous background, the other one generates the absorbing plasma. Several light element have been successsively introduced in the spark anode. For all of them new autoionizing levels have been observed in Rydberg series of resonances exhibiting the asymmetric ‘Beutler-Fano’ profile.In the beryllium and magnesium spectra three new series corresponding to two-electron excitation process have been identified while for boron, carbon, nitrogen, aluminium and silicon the resonances observed correspond to single subshell electron excitation such as: 2s22p2P0 → 2s2p(3P0)np2De for the case of boron.All these series lie in the photoionization continuum of the absorbing atomic species and usually between the first and second ionization limit. This means that they were observed with a normal incidence grating spectrograph in the spectral range 500–1500 Å. In the extreme ultraviolet some other transitions involving inner-shell electron excitation were observed. In the beryllium spectra a series lying between 100 and 110 Å was identified while, the magnesium spectra exhibited only isolated resonances in the 220-265 Å range together with an inner-shell 2p electron photoioniation continuum.A complete description of experimental results with numerical data is being submitted for publication (Esteva and Mehlman-Balloffet, 1972).


1978 ◽  
Vol 56 (7) ◽  
pp. 962-973 ◽  
Author(s):  
Yumio Morioka ◽  
Harunobu Masuko ◽  
Masatoshi Nakamura ◽  
Michio Sasanuma ◽  
Eiji Ishiguro

The absorption coefficients of NO2 in the region from 500 to 1100 Å are measured by a photographic method using the radiation from electron synchrotron as a background source. For the Rydberg series due to the transition from 4a1 to npπ, parameters q and Γ in Mies equation are obtained and the parameter q is determined to be −0.4 for every member and Γ 4.808/n*3 eV where n* is the effective quantum number.The absorption spectrum of NO2 in the region from 600 to 1600 Å are also analyzed. New vibrational progressions that are observed around 950 Å, are assigned to the excitations from 4b2 to ns Rydberg states (n = 3, 4, and 5) converging to the 1B2 ionic state. Assignments and discussions of many other Rydberg series that appear in the absorption spectrum between 600 and 1600 Å are also presented.


1979 ◽  
Vol 57 (10) ◽  
pp. 1650-1661 ◽  
Author(s):  
A. E. Douglas ◽  
F. R. Greening

The absorption spectra of HCl and HF have been photographed at high dispersion in the vacuum ultraviolet region. In the HCl spectrum, many new band systems have been identified and 18 vibrational levels of the ionic B1Σ state have been observed. The B1Σ state is found to interact strongly with the Rydberg states. Although many bands have been analysed, much of the HCl spectrum remains unassigned. Analyses of bands associated with the lowest discrete 1Π and 3Π states of HF are presented together with the analyses of two 1Π–X1Σ band systems which lie between the first and second ionization limit. The spectrum of HF is very complex and little of it has been analysed even though the spectral lines are sharp and well resolved. The theoretical problems in understanding the spectra of HCl and HF are discussed.


1968 ◽  
Vol 21 (9) ◽  
pp. 2153 ◽  
Author(s):  
JG Angus ◽  
BJ Christ ◽  
GC Morris

The vapour absorption spectra of naphthalene and naphthalene-d8 were obtained photographically and photoelectrically from 50000 to 70000 cm-1. A series of Rydberg transitions and possibly two π*-π systems are observed. Each of the five Rydberg series converges to an ionization potential of 65620 � 40 cm-l, i.e. 8.136 � 0.005 eV (C10H8), and 65640 � 60 cm-l, i.e. 8.138 � 0.008 eV (C10D8). The quantum defects of the series are (0.94, 0.88, 0.82, 0.67, 0.53) � 0.01. The significance of these results is discussed.


1956 ◽  
Vol 34 (6) ◽  
pp. 596-615 ◽  
Author(s):  
P. G. Wilkinson

The absorption spectra of benzene and benzene-d6 have been photographed from 1300 Å to 1850 Å in the first order of a 21-ft. normal incidence vacuum spectrograph. The band analysis resulted in the identification of four Rydberg series (over one hundred vibrational bands) in each molecule, converging to ionization potentials of 9.247 ev. (benzene) and 9.251 ev. (benzene-d6). Progressions of the ν2, ν18, and ν20 vibrations are associated with most of the 31 observed Rydberg transitions, and vibrational constants are tabulated for each. The strong intensity and the unusual length of the upper state ν18 (e2g) progression in comparison with the ν2(a1g) progression are interpreted in terms of the Jahn–Teller theorem, and it is concluded that the stable equilibrium nuclear configuration in the Rydberg states is of D2h symmetry.


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