Probabilities of optical transitions in electronic vibration-rotation spectra of diatomic molecules

Kuznetsova, L. A.; Кузьменко, Н.Е.; Kuzyakov, Yu. Ya.; Plastinin, Yu. A.

doi:10.1070/pu1974v017n03abeh004141

Cited by 52 publications

(17 citation statements)

References 6 publications

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“…The maximum differences between the centrifugal constants calculated from Eqs. (11) and (12) and on the basis of the Morse potential curve are equal to 0.1 and 2.3% for the ground state and 0.2 and 5.1% for the excited state, respectively. Conclusions.…”

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

“…where S e (r v ′ v ′′) is the dependence of the electron transition strength on the r centrode; r v ′ v ′′ is the r centrode, i.e., the mean internuclear distance, which is put into the correspondence for the electronic-vibrational band [11]; q v ′ v ′′ is the Franck-Condon factor, and ν v ′ v ′′ is the wave number of the electronic-vibrational band. The Franck-Condon factors and r centrodes for AgAu are lacking in the literature.…”

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

“…The expression that determines the coupling between the lifetime of the excited electronic-vibrational level and the strength of the electron transition A-X has the form [11] τ ν ′ −1 = (64π…”

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

“…The rotational constants B e and α e were also calculated from Eq. (1) and from the relation of Pekeris [14]: the centrifugal constants were found from the relation of Kratzer [15]: D e = 4B e 3 ⁄ ω e 2 (11) and from the relation of Kemble et al [16]:…”

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

“…states of AgAu just as for CuAg and CuAu [6,7], the following Morse potential function, well-known in molecular spectroscopy, was used [11,12]:…”

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confidence: 99%

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Calculation of the Spectroscopic Constants and Strength of the Electron Transition A0+-X 1Σ+ of the AgAu Molecule

Smirnov

2005

J Appl Spectrosc

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539.194 The vibrational, rotational, and centrifugal constants for the electronic states A and X 1 Σ + of the AgAu molecule have been calculated. The calculation is based on the Morse potential functions that were used to approximate the real potential curves of the ground and excited states of AgAu. Using the experimental data on the lifetime of the vibrational levels of the excited electronic state, the strength of the A-X transition was calculated.Keywords: potential curve; radial wave equation; vibrational, rotational, and centrifugal constants; electron transition strength.Introduction. Clusters of transition metals are finding wide practical application as effective catalysts of heterogeneous processes, and they also are important components of highly sensitive sensory systems. This explains the high interest in the study of the electronic structure of these clusters. From the viewpoint of the electronic structure, small clusters (dimers) of transition metals are the simplest ones.In his previous works, the present author calculated the spectroscopic constants for the ground and excited electronic states as well as the factors of the Franck-Condon dimers (Cu 2 , Ag 2 , Au 2 ) [1-5] and of mixed dimers (CuAg, CuAu) [6, 7] of the atoms of the 1st-group transition metals from the periodic table of elements. The calculations were performed by the quantum-chemical method on the basis of semiempirical potential curves. Comparison between the predicted and experimental vibrational, rotational, and centrifugal constants has proved the high accuracy of the method of calculation of molecular constants. In the present work, the spectroscopic constants are calculated for the ground (X 1 Σ + ) and excited (A0 + ) electronic states of the AgAu molecule, the characteristic feature of which is a more complex structure of the spectrum in comparison with the earlier considered biatomic heteronuclear molecules [6,7], which is due to the higher density of the electronic, vibrational, and rotational energy levels.Investigations of the spectrum of the A0 + -X 1 Σ + transition of 107 Ag 197 Au by various laser methods, the technique of supersonic molecular beams, and selective mass spectrometry were carried out in [8,9]. Only vibrational constants for combining states were determined. The spectral resolution appeared insufficient for studying the rotational structure of the electronic-vibrational bands and obtaining rotational constants.Construction of Potential Curves. To construct the semiempirical potential curve of a biatomic molecule, experimental data on its vibrational and rotational constants are needed. As was noted, there are no experimental data on rotational data for the X 1 Σ + -and A states of AgAu; therefore in the present work, using the experimental values of the equilibrium internuclear distances of the basic electronic states of Ag 2 [10] and Au 2 [8], the equilibrium internuclear distance for the ground state r e (X 1 Σ + ) of AgAu was estimated by the additivity rule as 2.501 A°. Preliminary calculations ...

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Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

Section: Calculation Of the Electron Transition Strengthmentioning

confidence: 99%

“…states of AgAu just as for CuAg and CuAu [6,7], the following Morse potential function, well-known in molecular spectroscopy, was used [11,12]:…”

mentioning

confidence: 99%

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Calculation of the Spectroscopic Constants and Strength of the Electron Transition A0+-X 1Σ+ of the AgAu Molecule

Smirnov

2005

J Appl Spectrosc

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Resonant and Near‐Resonant Rayleigh and Raman Scattering for a Diatomic Molecule

Berg¹,

Robinson

1977

Israel Journal of Chemistry

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Using the results of a unified theory of scattering in the time‐independent (narrow exciting line) limit, excitation profiles for Rayleigh and Raman cross sections have been calculated for an actual diatomic molecule from over 8000 cm−1 off resonance into the resonance region. Three interference effects, a “vibrational level interference”, an “on‐resonance Franck—Cordon interference”, and “off‐resonance interference,” are discussed.

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Morse matrix elements: An asymptotic expansion treatment

Chakraborty

1982

Int J of Quantum Chemistry

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An asymptotic expansion method has been used to calculate the Morse matrix elements for the vibration-rotation transition. A general expression has been derived for the quartic matrix elements, which can be reduced to the expressions for the cubic, quadratic, and linear matrix elements. The results agree extremely well with those given by the factorization method outlined by Badawi et al., and are similar to those given by Coquant et al., who used quite complicated and lengthy equations based on the Dunham potential. Earlier works to calculate the electronic transition probability parameters utilizing the above mentioned asymptotic expansion technique have also been extended and modified.

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Probabilities of optical transitions in electronic vibration-rotation spectra of diatomic molecules

Cited by 52 publications

References 6 publications

Calculation of the Spectroscopic Constants and Strength of the Electron Transition A0+-X 1Σ+ of the AgAu Molecule

Calculation of the Spectroscopic Constants and Strength of the Electron Transition A0+-X 1Σ+ of the AgAu Molecule

Resonant and Near‐Resonant Rayleigh and Raman Scattering for a Diatomic Molecule

Morse matrix elements: An asymptotic expansion treatment

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