Molecular electron energy levels

Location of molecular electronic energy levels in relation to device properties... 

In 1935, after studying the luminescence of various colorants, Jablonski suggested the electronic energy diagram of the singlet and triplet states to explain the luminescence processes of excitation and emission. The proposed diagram of molecular electronic energy levels formed the basis of the theoretical interpretation of all luminescent phenomena [21],... 

Fig. 3.2 A hypothetical molecular electron energy level scheme is show with increasing binding energies downward. The corresponding photoelectron spectrum is simulated above, with increasing electron kinetic energies upward.

In Section 1.3 the shift of the single molecule excitation line under the influence of a static electric field, the DC Stark effect, is discussed. The interaction of molecular electronic energy levels with a strong optical field is also expected to lead to level shifts and splittings and additionally to a change of relaxation rates. The shift of energy levels under optical excitation is called light shift or AC Stark effect where... 

Figure 12.1 Molecular electron energy levels split in a solid.

Whereas the gas lasers described use energy levels characteristic of individual atoms or ions, laser operation can also employ molecular energy levels. Molecular levels may correspond to vibrations and rotations, in contrast to the electronic energy levels of atomic and ionic species. The energies associated with vibrations and rotations tend to be lower than those of electronic transitions thus the output wavelengths of the molecular lasers tend to He farther into the infrared. 

Meckler, A., J. Chem. Phys. 21, 1750, Electronic energy levels of molecular oxygen." Eight electrons Cl. (Is and 2s shells kept filled.) Gaussian type AO. 

In Chapter 10, we will make quantitative calculations of U- U0 and the other thermodynamic properties for a gas, based on the molecular parameters of the molecules such as mass, bond angles, bond lengths, fundamental vibrational frequencies, and electronic energy levels and degeneracies. 

Table A4.1 summarizes the equations needed to calculate the contributions to the thermodynamic functions of an ideal gas arising from the various degrees of freedom, including translation, rotation, and vibration (see Section 10.7). For most monatomic gases, only the translational contribution is used. For molecules, the contributions from rotations and vibrations must be included. If unpaired electrons are present in either the atomic or molecular species, so that degenerate electronic energy levels occur, electronic contributions may also be significant see Example 10.2. In molecules where internal rotation is present, such as those containing a methyl group, the internal rotation contribution replaces a vibrational contribution. The internal rotation contributions to the thermodynamic properties are summarized in Table A4.6.

FIGURE 3.31 Atypical molecular orbital energy-level diagram for the homonuclear diatomic molecules Li2 through N2. Each box represents one molecular orbital and can accommodate up to two electrons. 

The molecular orbital energy-level diagrams of heteronuclear diatomic molecules are much harder to predict qualitatitvely and we have to calculate each one explicitly because the atomic orbitals contribute differently to each one. Figure 3.35 shows the calculated scheme typically found for CO and NO. We can use this diagram to state the electron configuration by using the same procedure as for homonuclear diatomic molecules. 

FIGURE 3.37 The molecular orbital energy-level diagram for methane and the occupation of the orbitals by the eight valence electrons of the atoms. 

FIGURE 3.40 The molecular orbital energy-level diagram for SFf, and the occupation of the orbitals by the 12 valence electrons of the atoms. Note that no antibonding orbitals are occupied and that there is a net bonding interaction even though no d-orbitals are involved. 

For each of the following, draw a molecular orbital energy level diagram and give the bond order. Tell whether the species would be more or less stable after gaining an electron, (a) 02+ (b) CN (c) S2 (d) NO (e) Be2+. 

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