Rotational analysis of hydroxyl vibration–rotation emission bands: Molecular constants for OH X2Π, 6 ≤ ν ≤ 10

1982 ◽  
Vol 60 (1) ◽  
pp. 41-48 ◽  
Author(s):  
J. A. Coxon ◽  
S. C. Foster
Keyword(s):  
Hydroxyl Radical ◽  
Least Squares ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Rotational Analysis ◽  
Coupling Constant ◽  
Molecular Constants ◽  
Vibration Rotation ◽  
Measured Line

Seven vibration–rotation emission bands of the hydroxyl radical with 6 ≤ ν′ ≤10 have been recorded photoelectrically in the range λ6250–8500 Å. The first reliable constants for levels 6 ≤ ν ≤10 of OH X2Π are obtained by direct least-squares fitting of the measured line frequencies. The vibrational dependences of the Λ-doubling parameters (p and q) and the spin–orbit coupling constant (A) are well defined. A minimum value of Aν is found at ν = 7.

Electronic Spectrum of the N80Se Molecule in the Region 2840–3200 Å

1971 ◽  
Vol 49 (15) ◽  
pp. 2033-2051 ◽  
Author(s):  
L. Harding ◽  
W. E. Jones ◽  
K. K. Yee ◽  
A. Jenouvrier ◽  
D. Daumont ◽  
...  
Keyword(s):  
Electronic Spectrum ◽  
Ground State ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Rotational Analysis ◽  
Coupling Constant ◽  
Molecular Constants ◽  
First Time

The vibrational and rotational analysis of 12 red degraded bands of N80Se, in the region 2800 to 3200 Å, is reported. These bands are attributed to two progressions, ν′ = 1 and ν′ = 2, of the subsystem C2Δ5/2–X2Π3/2 and to two progressions, ν′ = 0, of the system B2Σ–X2Π(a).Tables of molecular constants of the observed states are given. For the first time it has been possible to calculate the spin–orbit coupling constant, Aeff, of the ground state, X2Π(a).

First rotational analysis of the A2Π-X2Π system of the P35Cl+ cation

1987 ◽  
Vol 65 (5) ◽  
pp. 980-983 ◽  
Author(s):  
John A. Coxon ◽  
Stavros Naxakis ◽  
Utpal K. Roychowdhury
Keyword(s):  
Least Squares ◽  
Band System ◽  
Coupling Constants ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Rotational Analysis ◽  
Entire Data

The visible A2Π → X2Π band system of PCl+ has been recorded photoelectrically with a resolution of 0.006 nm. Fourteen 2Π1/2–2Π1/2 and six 2Π3/2–2Π3/2 sub-bands of P35Cl+ in the ν′ = 0 and 1 progressions with 10 ≤ ν″ ≤ 20 have been rotationally analysed. The measured positions of 1214 lines have been fitted directly by least squares to obtain a set of reliable constants for the two states that reproduce the entire data. These constants include the first estimated spin–orbit coupling constants for both states. The reliability of these estimates is discussed. The equilibrium internuclear separations are re(X) = 0.1900 and re(A) = 0.2334 nm.

Electron resonance of SO ( 3 Ʃ ) in the gas phase

1967 ◽  
Vol 298 (1454) ◽  
pp. 340-358 ◽  
Keyword(s):  
Coupling Constants ◽  
Orbit Coupling ◽  
Spin Coupling ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Coupling Constant ◽  
Molecular Constants ◽  
Excited Vibrational State ◽  
Electron Resonance

The electron resonance spectrum of SO has been previously shown to arise from SO in two electronic states, the ground 3 Ʃ - and the excited 1 ∆ state. In this paper the portion of the spectrum assigned to the 3 Ʃ - state is analysed and shown to arise from three isotopic species, 32 S 16 O, 33 S 16 O, and 34 S 16 O. The analysis shows that besides the dominant interaction of the unpaired electronic spins with the magnetic field; other interactions must be taken into account to interpret the spectrum accurately. Interactions with electronic orbital angular momentum of π states mixed in by spin-orbit coupling and with rotationally induced magnetic moments have been observed. Values for parameters measuring such interactions have been determined from the spectrum, and these values lead to a resolution of the first- and second-order contributions to the zero-field molecular constants as well as an approximate value for the spin-orbit coupling constant. The hyperftne structure resulting from 33 S in 33 S 16 O has also been observed and is related to the usual hyperfine coupling constants. The expected line strengths and widths for SO have been calculated and these are compared with the observed quantities. Besides the expected lines from the isotopic SO species in the 3 Ʃ - state, several other lines have been detected. These lines are interpreted as arising from 32 S 16 O in the ground electronic state, but in the first excited vibrational level. The spectrum of vibrationally excited SO allows a value of the spin-spin coupling constant in the first excited vibrational state to be determined.

Rotational analysis of emission bands of the A2Πi–X2Πi system of 35ClO

1976 ◽  
Vol 54 (10) ◽  
pp. 1043-1052 ◽  
Author(s):  
J. A. Coxon ◽  
W. E. Jones ◽  
E. G. Skolnik
Keyword(s):  
Absorption Spectrum ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Rotational Analysis ◽  
Internuclear Separation ◽  
Molecular Constants

Five bands of the 0–ν″ progression (5 ≤ ν″ ≤ 9) of the A2Πi–X2Πi system of 35ClO have been rotationally analysed. The results have been combined with data from the absorption spectrum of ClO, and new molecular constants are reported. The variation of spin–orbit coupling with internuclear separation has been determined for both states.

Le spectre électronique de BS. Partie I : Analyse des perturbations du système A2Π–X2Σ+

1981 ◽  
Vol 59 (12) ◽  
pp. 1851-1861 ◽  
Author(s):  
A. Jenouvrier ◽  
B. Pascat
Keyword(s):  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Matrix Elements ◽  
Coupling Constant ◽  
Perturbation Matrix ◽  
Electronic Perturbation ◽  
Vibration Rotation ◽  
Π State

The deperturbed vibration–rotation constants of the A2Π and X2Σ+ states of BS are obtained. The perturbations in the levels of the A2Π state observed in the A2Π–X2Σ+ system are treated and are the result of interactions with high levels of the X2Σ+ state. The electronic factors of the spin–orbit and rotation–electronic perturbation matrix elements for the A ~ X interaction are evaluated. The deperturbed spin–orbit coupling constant of the A state is determined.

Ground configuration splitting in UCl5

1977 ◽  
Vol 55 (10) ◽  
pp. 937-942 ◽  
Author(s):  
A. F. Leung ◽  
Ying-Ming Poon
Keyword(s):  
Crystal Field ◽  
Energy Levels ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Coupling Constant ◽  
Point Charge Model ◽  
X Ray Crystallography ◽  
Charge Model ◽  
Crystal Field Parameters

The absorption spectra of UCl5 single crystal were observed in the region between 0.6 and 2.4 μm at room, 77, and 4.2 K temperatures. Five pure electronic transitions were assigned at 11 665, 9772, 8950, 6643, and 4300 cm−1. The energy levels associated with these transitions were identified as the splittings of the 5f1 ground configuration under the influence of the spin–orbit coupling and a crystal field of C2v symmetry. The number of crystal field parameters was reduced by assuming the point-charge model where the positions of the ions were determined by X-ray crystallography. Then, the crystal field parameters and the spin–orbit coupling constant were calculated to be [Formula: see text],[Formula: see text], [Formula: see text], and ξ = 1760 cm−1. The vibronic analysis showed that the 90, 200, and 320 cm−1 modes were similar to the T2u(v6), T1u(v4), and T1u(v3) of an UCl6− octahedron, respectively.

Magnetic Susceptibilities of 2T2 Ions. Part 1

1972 ◽  
Vol 50 (10) ◽  
pp. 1468-1471 ◽  
Author(s):  
Alan D. Westland
Keyword(s):  
Magnetic Susceptibility ◽  
Excited State ◽  
Reduction Factor ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Coupling Constant ◽  
Magnetic Susceptibilities

An expression for the magnetic susceptibility of octahedral d1 complexes is derived exactly in terms of an orbital reduction factor k taking into account the presence of the formal 2E excited state. Sample calculations show that the improved expression gives results for susceptibility which are lower at times by several percent from those given by previous expressions. The results given by Figgis using Kotani's method are adequately precise when the spin–orbit coupling constant is no larger than ~0.1 Dq.

High-resolution laser-excitation spectrum of the A2Π ← X2Σ system of TiN: rotational analysis of the 0–0, 1–1, and 2–2 bands

1985 ◽  
Vol 63 (7) ◽  
pp. 997-1004 ◽  
Author(s):  
K. Brabaharan ◽  
J. A. Coxon ◽  
A. Brian Yamashita
Keyword(s):  
High Resolution ◽  
Least Squares ◽  
Excitation Spectrum ◽  
Laser Excitation ◽  
Rotational Analysis ◽  
Molecular Constants ◽  
Individual Bands ◽  
Measured Line ◽  
Line Positions ◽  
Π State

The 0–0, 1–1, and 2–2 bands of the A2Π ← X2Σ system of TiN have been recorded using the technique of laser-excitation spectroscopy. Molecular constants have been obtained from direct least squares fits of the measured line positions of individual bands. The fitted constants confirm and extend previous determinations; for the A2Π state, some of the constants show unusually large variations with ν, in accord with the already known perturbation of this state in the ν = 0 level.

Magnetic circular dichroism studies of matrix‐isolated atoms: Excited state spin‐orbit coupling constant reduction of copper in the noble gases

1984 ◽  
Vol 80 (6) ◽  
pp. 2401-2406 ◽  
Author(s):  
Martin Vala ◽  
Kyle Zeringue ◽  
Jalal ShakhsEmampour ◽  
Jean‐Claude Rivoal ◽  
Robert Pyzalski
Keyword(s):  
Circular Dichroism ◽  
Excited State ◽  
Noble Gases ◽  
Magnetic Circular Dichroism ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Coupling Constant ◽  
State Spin ◽  
Circular Dichroïsm

Theory of spin-orbit coupling in atoms, II. Comparison of theory with experiment

1963 ◽  
Vol 271 (1347) ◽  
pp. 565-578 ◽  
Keyword(s):  
Wave Functions ◽  
Coupling Constants ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Outer Electron ◽  
Coupling Constant ◽  
Radial Wave ◽  
Order Of Magnitude ◽  
Experimental Values

Results of calculations of the spin-orbit coupling constant for 2 p , 3 p , 4 p , and 3 d shell ions and atoms are presented. The calculations are based on a theory developed in a previous paper. Excellent agreement of this theory with experiment is obtained for the 2 p and 3 d shell ions, while calculations using the familiar < ∂ V / r ∂ r > expression for the coupling constant lie 10 to 20 % too high. The exchange terms discussed in the earlier paper make a contribution to the coupling constant of the same sign and order of magnitude as the ordinary shielding terms. For the 3 p and 4 p shell atoms, the calculated coupling constants based on the exact theory and on the < ∂ V / r ∂ r > expression both tend to lie below the experimental values. An explanation for this disagreement is suggested, based on the noded nature of the outer-electron radial wave functions for these atoms. The importance of the residual-spin-other-orbit interaction is discussed, and it is shown that ignoring the form of this interaction may lead to a large variation in the coupling constant within a configuration.

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