Internal electron excitation

These results do not agree with experimental results. At room temperature, while the translational motion of diatomic molecules may be treated classically, the rotation and vibration have quantum attributes. In addition, quantum mechanically one should also consider the electronic degrees of freedom. However, typical electronic excitation energies are very large compared to k T (they are of the order of a few electronvolts, and 1 eV corresponds to 10 000 K). Such internal degrees of freedom are considered frozen, and an electronic cloud in a diatomic molecule is assumed to be in its ground state f with degeneracy g. The two nuclei A and... 

A-B relative or external motion undergo free-free transitions (E., E. + dE.) (Ej Ej+ dE within the translational continuum, while the structured particles undergo bound-bound (excitation, de-excitation, excitation transfer) or bound-free (ionization, dissociation) transitions = (a, 3) ->/= (a, (3 ) in their internal electronic, vibrational or rotational structure. The transition frequency (s ) for this collision is... 

In (a), an ion and a gas atom approach each other with a total kinetic energy of KE, + KEj. After collision (b), the atom and ion follow new trajectories. If the sum of KE, + KEj is equal to KE3 + KE4, the collision is elastic. In an inelastic collision (b), the sums of kinetic energies are not equal, and the difference appears as an excess of internal energy in the ion and gas molecule. If the collision gas is atomic, there can be no rotational and no vibrational energy in the atom, but there is a possibility of electronic excitation. Since most collision gases are helium or argon, almost all of the excess of internal energy appears in the ion. 

Interestingly, it was possible to probe the spin-forbidden component of the tunneling reaction with internal and external heavy atom effects. Such effects are well known to enhance the rates of intersystem crossing of electronically excited triplets to ground singlet states, where the presence of heavier nuclei increases spin-orbit coupling. Relative rates for the low-temperature rearrangements of 12 to 13 were... 

A distinguishing feature of electronically excited atoms and molecules is that they have one or a few excited orbitals of an electron. The principal properties of these particles are represented by a high internal energy potential localized on the excited orbitals and the structure of electron shell essentially different from the electron ground state. 

Pecourt J-ML, Peon J, Kohler B (2000) Ultrafast internal conversion of electronically excited RNA and DNA nucleosides in water. J Am Chem Soc 122 9348... 

Zgierski MZ, Patchkovskii S, Fujiwara T, Lim EC (2005) On the origin of the ultrafast internal conversion of electronically excited pyrimidine bases. J Phys Chem A 109 9384-9387... 

Electronic excitation of the chromophore is simulated by instantly switching the charges (and in some studies also the geometry) on the QM system to excited state (Sj) values. Most of the internal Stark effect (ISE) is expressed implicitly by the difference of the potentials at different atoms. 

The rate constant ke corresponds to the reciprocal of the lifetime of the excited state. Internal conversion The excited state can do other things, such as convert some of the original electronic excitation to a mixture of vibration and a different electronic state. These are also treated as unimolecular processes with associated rate constants ... 

We saw in the last section that because of the rapid nature of vibrational relaxation and internal conversion between excited states an electronically-excited molecule will usually relax to the lowest vibrational level of the lowest excited singlet state. It is from the Si(v = 0) state that any subsequent photophysical or photochemical changes will generally occur (Kasha s rule). 

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