Electric dipole-forbidden

It should also be remembered that the selection mles derived here are relevant to the free molecule and may break down in the liquid or solid state. This is the case, for example, with the electric dipole forbidden 4q transition in ethylene, where V4 is the torsional vibration shown in Figure 6.23. It is not observed in the infrared specttum of the gas but is observed weakly in the liquid and solid phases. 

A < 640 nm (or 1.9 < E < 2.5 eV), weak absorption takes plaee, and is associated with electric dipole-forbidden transitions between the one-electron HOMO level w ith /i symmetry and the one-electron Uu LUMO level. 

E and E. Transitions from the ground A, state to the E state is dipole allowed, but transitions to all the triplet states are spin-forbidden. The Aj Aj, and the Ai A2 transitions are electric dipole-forbidden but become allowed by vibrcnic coupling to the E level. A vibration of t or symmetry makes the former absorption allowed, while the latter is allowed only by a vibration of e symmetry. 

The characteristic absorption and emission spectra of lanthanide compounds in the visible, near ultra-violet and infra-red is attributed to transitions between 4/ levels due to the fact that they present a sharp line with oscillators strengths typically of the order of 10 . These transitions are electric dipole forbidden but became allowed as forced electric dipole transitions. 

By reference to the MO scheme in Fig. 2, the bands at X < 400 nm have been assigned to sharp and intense parity-allowed transitions between occupied (bonding) and empty (antibonding) MOs. Such excitations include Au(HOMO)— fJg(LUMO + 1) and hg—> Optical transitions between the HOMO(Au) and LUMO(f/u), which are electric dipole forbidden, occur via excitation of a vibronic state with appropriate parity symmetry and account for the broad and low intensity band at X > 400 nm. 

The efficiency of photon capture to form the l(nn ) state is very low since the excitation is electric dipole forbidden in the local C2V point group of the carbonyl. Direct... 

Specifically, the collision-induced absorption and emission coefficients for electric-dipole forbidden atomic transitions were calculated for weak radiation fields and photon energies Ha> near the atomic transition frequencies, utilizing the concepts and methods of the traditional theory of line shapes for dipole-allowed transitions. The example of the S-D transition induced by a spherically symmetric perturber (e.g., a rare gas atom) is treated in detail and compared with measurements. The case of the radiative collision, i.e., a collision in which both colliding atoms change their state, was also considered. 

The transition dipole moment functions are — like the potentials — functions of Q. Their magnitudes determine the overall strength of the electronic transition ki —> kf. If the symmetry of the electronic wavefunc-tions demands likfki to be exactly zero, the transition is called electric-dipole forbidden. The calculation of transition dipole functions belongs, like the calculation of the potential energy surfaces, to the field of quantum chemistry. However, in most cases the fikfkt are unknown, especially their coordinate dependence, which almost always forces us to replace them by arbitrary constants. 

Figure 24 displays the high energy (E > 25,000 cm-1) region of the room temperature electronic absorption spectrum for Zn(bpy)(tdt), where bpy = 2,2 -bipyridine. The LLCT transition occurs at 22,470 cm-1 (445 nm) with very weak absorption intensity (e = 72 M 1cm 1). The origin of the weak LLCT is a function of the symmetry of this psuedo-tetrahedral complex. A MO diagram for Zn(bpy)(tdt), derived from extended Hiickel calculations, is presented in Fig. 25. Irrespective of whether the metallo(diimine)(dithiolene) complex is square-planar or psuedo-tetrahedral, the point symmetry is C2V, and all intermediate geometries possess C2 symmetry. When the dithiolene and diimine planes are orthogonal (psuedo-tetrahedral geometry) the HOMO — LUMO transition represents a b2 —> b one-electron promotion and is electric dipole forbidden. However, the HOMO —> LUMO transition in a square-planar...

Electronic Transitions. Since formaldehyde (H2C0) is the simplest carbonyl compound, the CO ir +- n electronic transition of the carbonyl compounds will be briefly described using the formaldehyde transition as the prototype. The lowest singlet state of the CO chromophore of an unconjugated carbonyl can be produced by one-photon absorption of light between 360 and 240 rim (46). This electronic transition is weak, with typical maximum decadic molar extinction coefficient (e) of less than 2 x 10 liters/mol cm. This transition corresponds to the well-known electric-dipole-forbidden vibronically allowed X A ... 

The ultraviolet spectroscopy of formaldehyde has been studied almost exhaustively, and there is an excellent review on this subject (171). A majority of the bands in the electric-dipole-forbidden vibronically allowed A 2 +X Aj transition have been assigned mostly due to the work of Brand (37), Robinson and DiGiorgio (196), Callomon and Innes (44), and Job, et al. (124). As briefly mentioned earlier, the ground electronic state (X) is planar and the first excited singlet state (A) is pyramidal. It is valid to use the C2V point group symmetry for both electronic states, rather than the C2 point group symmetry (see ref. 171), although the emission could certainly be treated as a -A" - 1A transition. 

The narrow absorption and emission bands of rare-earth 0-diketonates in the visible, near ultra-violet and near infra-red is attributed to 4f-4f transitions. These transitions are electric dipole forbidden to first order, but are allowed by the electric quadrupole, vibronic, magnetic dipole and forced electric dipole mechanisms. The magnetic dipole character of the Dq F transition of the Eu + ion was demonstrated in 1939 by... 

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