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This follows from the application of selection rules. [16] Resonance Raman spectroscopy involves a kind of vibronic coupling. It results in much-increased intensity of fundamental and overtone transitions as the vibrations "steal" intensity from an allowed electronic transition. [17] In spite of appearances, the selection rules are the same as ...
The Laporte rule is a rule that explains the intensities of absorption spectra for chemical species. It is a selection rule that rigorously applies to atoms, and to molecules that are centrosymmetric, i.e. with an inversion centre. It states that electronic transitions that conserve parity are forbidden. Thus transitions between two states that ...
For any given transition, the value of P is determined by all of the selection rules, however spin selection is the largest contributor, followed by electronic selection rules. The Franck–Condon factor only weakly modulates the intensity of transitions, i.e., it contributes with a factor on the order of 1 to the intensity of bands whose order ...
The lightest atom that requires the second rule to determine the ground state term is titanium (Ti, Z = 22) with electron configuration 1s 2 2s 2 2p 6 3s 2 3p 6 3d 2 4s 2. In this case the open shell is 3d 2 and the allowed terms include three singlets (1 S, 1 D, and 1 G) and two triplets (3 P and 3 F).
Together with the selection rules for an electric dipole transition, i.e., =, =, =, =, this allows to ignore the spin degree of freedom altogether. As a result, only three spectral lines will be visible, corresponding to the Δ m l = 0 , ± 1 {\displaystyle \Delta m_{l}=0,\pm 1} selection rule.
Schematic of energy levels involved in two photons absorption. In atomic physics, two-photon absorption (TPA or 2PA), also called two-photon excitation or non-linear absorption, is the simultaneous absorption of two photons of identical or different frequencies in order to excite an atom or a molecule from one state (usually the ground state), via a virtual energy level, to a higher energy ...
In rotational-vibrational and electronic spectroscopy of diatomic molecules, Hund's coupling cases are idealized descriptions of rotational states in which specific terms in the molecular Hamiltonian and involving couplings between angular momenta are assumed to dominate over all other terms.
Then, the rule is that the amount of energy absorbed by an electron may allow for the electron to be promoted from a vibrational and electronic ground state to a vibrational and electronic excited state. A third rule is the Laporte Rule, which necessitates that the two energy states between which an electron transitions must have different ...