scholarly journals VIBRATION-ROTATION INTERACTION FACTORS FOR DIATOMIC MOLECULES CALCULATED BY NUMERICAL METHODS

1963 ◽  
Author(s):  
J Cashion
Keyword(s):  
Numerical Methods ◽  
Diatomic Molecules ◽  
Interaction Factors ◽  
Vibration Rotation

INFLUENCE OF VIBRATION–ROTATION INTERACTION ON THE INTENSITIES OF PURE ROTATION LINES OF DIATOMIC MOLECULES

1956 ◽  
Vol 34 (11) ◽  
pp. 1119-1125 ◽  
Author(s):  
Robert Herman ◽  
Robert J. Rubin
Keyword(s):  
Line Intensity ◽  
Anharmonic Oscillator ◽  
Diatomic Molecules ◽  
Potential Energy Function ◽  
Complete Agreement ◽  
Contact Transformation ◽  
First Order ◽  
Pure Rotation ◽  
Rotation Line ◽  
Vibration Rotation

The magnitude of the effect of the vibration–rotation interaction on the intensities of pure rotation lines of diatomic molecules has been calculated for two different molecular models, the anharmonic oscillator and the rotating Morse or Pekeris oscillator. The intensity correction for the anharmonic oscillator has been obtained by adapting the contact transformation formalism for calculating second-order corrections to the energy to the calculation of first-order corrections to the matrix elements of the electric moment as suggested by H. H. Nielsen. The correction to the line intensity for vibrationless transitions of the anharmonic oscillator is found to be[Formula: see text]The results obtained here are also in complete agreement, to first order, with the results obtained earlier by Herman and Wallis for the 1–0 and 2–0 vibration–rotation line intensities. In the case of the Pekeris or rotating Morse oscillator the correction to the pure rotation line intensity is of the same form as above, namely,[Formula: see text]but exhibits minor differences which can be explained in terms of the difference in the vibrational potential energy function in the two cases.

Pressure broadening studies on vibration-rotation bands III. Experimental methods for determining line widths

1963 ◽  
Vol 272 (1351) ◽  
pp. 441-452 ◽  
Keyword(s):  
Diatomic Molecules ◽  
Experimental Methods ◽  
Pressure Broadening ◽  
Line Widths ◽  
Vibration Rotation

The basis of experimental methods for determining the line widths in vibration-rotation bands of diatomic molecules when broadened by foreign gases is explained. These involve the measurement of the relative self- and foreign-gas-broadening coefficients, of the 'equivalent’ line widths, or of the peak absorbance values of lines across a band. Some results on selfbroadening of CO, and DCl are compared with previous data.

RKR-type inversion of the diatomic energy shifts due to breakdown of the Born–Oppenheimer approximation

2004 ◽  
Vol 82 (6) ◽  
pp. 820-825 ◽  
Author(s):  
James KG Watson
Keyword(s):  
Diatomic Molecule ◽  
Internuclear Distance ◽  
Diatomic Molecules ◽  
Isotope Effects ◽  
Electron Mass ◽  
Effective Hamiltonian ◽  
Expectation Values ◽  
Oppenheimer Approximation ◽  
Vibration Rotation

The principal effects of the breakdown of the Born–Oppenheimer approximation on the vibration–rotation energies of a diatomic molecule can be represented by the expectation values of terms to order (me/Mi) in the effective Hamiltonian, where me is the electron mass and Mi is the mass of atom i. This paper examines the possibility of inverting these expectation values to obtain the correction functions as functions of the internuclear distance r, using a generalization of the semiclassical Rydberg–Klein–Rees method. It is shown that the correction functions are not completely determinable from the inversion, and the form of the determinable combinations is obtained.Key words: diatomic molecules, vibration–rotation energies, isotope effects, Born–Oppenheimer breakdown, Rydberg–Klein–Rees method.

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