Where does overtone intensity come from?
- 1 November 1990
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 93 (9) , 6140-6147
- https://doi.org/10.1063/1.458985
Abstract
The factors that influence overtone intensity are examined using realistic potential and dipole moment functions that model the acetylenic stretching vibration. It is found that mechanical anharmonicity is more important than electrical anharmonicity, especially at higher overtone levels but a quantitative treatment requires both contributions which are not simply additive. It is found numerically that the inner wall of the potential dominates in determining overtone intensity. This can be justified by heuristic arguments and by the properties of the sensitivity functional of the transition dipole matrix elements to changes in V(r). It is suggested that absolute overtone intensities could be useful in determining the inner walls of hydrogen stretching vibrations.Keywords
This publication has 19 references indexed in Scilit:
- The absolute intensity of visible overtone bands of acetyleneThe Journal of Chemical Physics, 1989
- Anharmonic potential-energy surfaces, vibrational frequencies and infrared intensities calculated from highly correlated wavefunctionsJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 1988
- The intensities of HCN overtone transitions from 12 600–18 400 cm−1The Journal of Chemical Physics, 1987
- Group additivity and overtone intensities for the isolated CH chromophoreChemical Physics Letters, 1984
- Comments on the concept of universal intensities in local mode theoryThe Journal of Chemical Physics, 1979
- Local mode overtone intensities of C–H stretching modes in alkanes and methyl substituted benzenesThe Journal of Chemical Physics, 1979
- Overtone emission spectroscopy of HF and DF: Vibrational matrix elements and dipole moment functionThe Journal of Chemical Physics, 1976
- The hydroxyl bands in the nightglowPlanetary and Space Science, 1963
- Dipole Moment Function of Diatomic MoleculesThe Journal of Chemical Physics, 1959
- Quantitative Absorptionsmessungen an den CH-Oberschwingungen einfacher KohlenwasserstoffeThe European Physical Journal A, 1935