Personal Finance: There Are No Shortcuts to Financial Security

Yarkony, Kathryn

doi:10.1016/j.aorn.2009.07.024

Cited by 1 publication

(1 citation statement)

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“…This approximate result is in agreement with DYIP's calculation which treated all vibrational modes. 45 This result is indeed also in accord with the experimental observations. With the parameterized form of the PES we see that unless the wells outside the C s plane are so deep as to largely localize the eigenfunction, the lowest eigenfunction will continue to transform as a as long as the in-plane barrier TS1 is higher than the in-plane minimum, min1.…”

Section: The Vibronic Hamiltonian Eigenvalues and Eigenfunctionssupporting

confidence: 88%

Rotationally resolved ${\tilde{B}} \leftarrow {\tilde{X}}$B̃←X̃ electronic spectra of the isopropoxy radical: A comparative study

Liu

Melnik

Miller

2013

The Journal of Chemical Physics

112

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The B̃-X̃ laser-induced-fluorescence spectrum of jet-cooled isopropoxy radical (i-C3H7O[middle dot]) has been recorded. Using an isolated state model the observed rotational and fine structure of the origin band has been well simulated to determine rotational constants for both the X̃ and B̃ states and the electron spin-rotation constants of the X̃ state. The line intensities are well simulated with a parallel transition type, requiring the same symmetry for the levels involved of each the X̃ and B̃ state, which confirms the previous suggestion that going from ethoxy (C2H5O[middle dot]) to isopropoxy, the energy ordering of the electron configurations with in- and out-of-plane half-filled p-orbitals of the oxygen atom is reversed and the ground vibronic symmetry changes from a" to a'. However, the observed spin-rotation coupling constants are not consistent with their predication from either semi-empirical theory or quantum chemical calculations. Additionally, the lack of observed transitions involving the out-of-plane transition moment component is not consistent with high level electronic structure calculations suggesting mixing of vibronic levels by strong spin-orbit coupling. A new twofold model has been developed that explicitly includes Coriolis and spin-orbit coupling between different vibronic levels. This model renders the discrepancy between theoretical and experimental spin-rotation constants moot. Moreover, it determines independently the contributions to the observed splitting between the lowest two levels, resulting from non-relativistic kinetic and Coulombic effects, and that due to the relativistic spin-orbit interaction. The experimental values show that these effects are comparable, but that the vibronic one is slightly more important. This result is at variance with state-of-the-art electronic structure calculations which otherwise do a remarkably good job of describing the ground state of isopropoxy.

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Section: The Vibronic Hamiltonian Eigenvalues and Eigenfunctionssupporting

confidence: 88%