Dispersed Fluorescence Spectrum of the A-X Electronic Transition in CFBr

The data file simulates the vibrational structure of the dispersed fluorescence spectrum obtained by exciting v₂ = 1 in the A state of CFBr. (See Rotational Structure of the A-X electronic transition in CFBr for the rotational structure.) The data file is a reasonably straightforward example of simulating vibrational structure. Notes:

• The ⁷⁹Br/⁸¹Br isotope splitting was not resolved in the dispersed fluorescence spectrum, so the set-up is for the average of the two.
• The x₁₃ and x₂₃ terms in the ground state must be included using perturbations.
• The vibrational mode displacements were determined by empirical fitting, so no information about the nuclei have been entered.
• A dispersed fluorescence rather than an absorption spectrum is simulated by setting Initial to false for the ground state manifold (X) and true for the upper state manifold (A).

This file also provides an example of using a Non-Boltzmann Population to simulate fluorescence from v₂ = 1 rather than v₂ = 0 that a Boltzmann population would imply. This was set up by:

1. Use "View","States" to bring up the State Details Window.
2. Select the A state in the Active Object combo box at the top of the window.
3. Right click on the required state in the "Eigenvalues" pane (the lower matrix), here state number 2 "0,1,0", and select "Add to population selection".
   
4. The required population is now a parameter in the A state manifold object.
5. To use the manually entered populations rather than a Boltzmann population, set the temperature negative.

Note that a similar effect can be obtained using vMin and vMax for various modes, though an implementation restriction in the current version means that values of vMin > 0 are likely to slow calculations for intensities considerably.

Dispersed fluorescence spectrum from v₂ = 1: