INDEX ground electronic states

The time-dependent wavepacket constructed in Section 4.1 is not the wavepacket that a laser with finite duration creates in the excited electronic state. It represents the wavepacket created by a pulse with infinitely narrow width in time. In order to construct the real wavefunction of the molecular system we must go back to Section 2.1. For simplicity of presentation, let us consider a diatomic molecule with internuclear separation R. We assume that the excitation takes place from the electronic ground state (index 0) to a bound upper state (index 1). The extension to a dissociative state, several coupled excited states, or several degrees of freedom is formally straightforward. 

The energy and structure parameters listed in the tables of this review belong in general to the v=0 vibrational state their notation is r0 for the interatomic distance, T0 for the 0-0 excitation energy. Vibrational frequencies v" are those of the lower (usually ground) state while v is the notation for the upper electronic states. Equilibrium parameters refering to the potential minimum and only available for diatomics are indexed by e (re, coe,xe). toe, xe and vv are connected by the equation... 

Here is the exact total energy of the system, are solutions of the Hartree-Fock problem, and e is the sum of Hartree-Fock orbital energies over occupied spinorbitals. Then the eigenvalue in eqn. (4.66), E, becomes directly the correlation energy in the i th electronic state. Since our concern is focused on the ground state, i.e. i B 0, the index i in eqn, (4.70) may be dropped and the respective contributions to the correlation energy can be expressed as... 

Using LIF detected OODR techniques Koperski and Czajkowski [03Kop] have investigated the electronic state which shows a deep potential well at 284 pm and a shallow one near 560 pm. Starting from the AO o = 0 vibronic ground state some series of levels have been excited via the intermediate levels A0 = 5 or / lo" =o,i,2 The parameters determined for the first minimum carry the index in, for the second one the index out in the listing below. 

In Eq. (7.1), states A and B are the two electronic states ground and excited states associated with the conical intersection, is the yth mass-weighted Cartesian coordinate of the t th atom, the index i labels the N atoms and y the Cartesians components, x, y, and z. These quantities are in principle obtainable only from a theoretical calculation. Nevertheless, as we shall discuss subsequently, they have a simple interpretation and one can often make a reasonable guess as to the nature of these two vectors using qualitative valence bond theory. 

Ionization Potential (IP), Electron Affinity (EA), Maximal Charge Acceptance ANmax, and Electrophilicity Index Ground State for the First and Second Row Atoms (Units in eV)... 

Brown (1959) has presented a charge transfer model of the transition state for electrophilic reactions which differs appreciably from that proposed by Fukui and his collaborators and leads to the definition of a new reactivity index termed the Z value . The model is based on a more conventional formulation of the charge transfer mechanism, which avoids the complete transfer of electrons associated with v = 0,1,2 in Fukui s model. There is no dependence on the formation of a pseudo tt orbital in the transition state, nor is hyperconjugation invoked. A wave function for a charge transfer complex is written as a linear combination of a wave function < o describing the unperturbed ground state of the molecule under attack, and a function which differs from (Pq in the replacement... 

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