The object now will be to steer the wavefunction out of a specific exit chaimel on the ground electronic state, using the excited electronic state as an intennediate. Insofar as the control is achieved by transferring amplitude between two electronic states, all tire concepts regarding the central quantity introduced above will now come into play. [Pg.269]

Tannor D J, Rice S A and Weber P M 1985 Picosecond CARS as a probe of ground electronic state intramolecular vibrational redistribution J. Chem. Phys. 83 6158... [Pg.280]

Weitz E and Flynn G W 1981 Vibrational energy flow in the ground electronic states of polyatomic molecules Adv. Chem. Rhys. 47 185-235... [Pg.1084]

The selection rule for vibronic states is then straightforward. It is obtained by exactly the same procedure as described above for the electronic selection rules. In particular, the lowest vibrational level of the ground electronic state of most stable polyatomic molecules will be totally synnnetric. Transitions originating in that vibronic level must go to an excited state vibronic level whose synnnetry is the same as one of the coordinates, v, y, or z. [Pg.1138]

An interesting example occurs in the spectrum of the C2 molecule. The usual rule of absorption spectroscopy is that the transitions originate in the ground electronic state because only it has sufficient population. However, in C2 transitions were observed starting both from a fl state and from a jTstate, so it was not... [Pg.1141]

The siim-over-states method for calculating the resonant enlrancement begins with an expression for the resonance Raman intensity, /.y, for the transition from initial state to final state /in the ground electronic state, and is given by [14]... [Pg.1161]

We note that the expression in brackets is just the b c tensor element of the electronic polarizability in the ground electronic state,, (ttj)- Thus... [Pg.1192]

Since the vibrational eigenstates of the ground electronic state constitute an orthonomial basis set, tire off-diagonal matrix elements in equation (B 1.3.14) will vanish unless the ground state electronic polarizability depends on nuclear coordinates. (This is the Raman analogue of the requirement in infrared spectroscopy that, to observe a transition, the electronic dipole moment in the ground electronic state must properly vary with nuclear displacements from... [Pg.1192]

infrared spectroscopy usually provide the most detailed picture of the vibration-rotation energy levels in the ground electronic state. However, they are not always possible and other spectroscopic methods are also important. [Pg.2447]

Equations (C3.4.5) and (C3.4.6) cover the common case when all molecules are initially in their ground electronic state and able to accept excitation. The system is also assumed to be impinged upon by sources F. The latter are usually expressible as tlie product cr

As was shown in the preceding discussion (see also Sections Vin and IX), the rovibronic wave functions for a homonuclear diatomic molecule under the permutation of identical nuclei are symmetric for even J rotational quantum numbers in and E electronic states antisymmeUic for odd J values in and E elecbonic states symmetric for odd J values in E and E electronic states and antisymmeteic for even J values in Ej and E+ electeonic states. Note that the vibrational ground state is symmetric under pemrutation of the two nuclei. The most restrictive result arises therefore when the nuclear spin quantum number of the individual nuclei is 0. In this case, the nuclear spin function is always symmetric with respect to interchange of the identical nuclei, and hence only totally symmeUic rovibronic states are allowed since the total wave function must be symmetric for bosonic systems. For example, the nucleus has zero nuclear spin, and hence the rotational levels with odd values of J do not exist for the ground electronic state f EJ") of Cr. [Pg.575]

However, drastic consequences may arise if the nuclear spin is 0 or In these cases, some rovibronic states cannot be observed since they are symmetry forbidden. For example, in the case of C 02, the nuclei are spinless and the nuclear spin function is symmetric under permutation of the oxygen nuclei. Since the ground electronic state is only even values of J exist for the ground vibrational level (vj, V3) = (OO O), where (vi,V2,V3) are the... [Pg.580]

Consider an N2 molecule, in the ground vibrational level of the ground electronic state, which is bombarded by 100 eV electrons. This leads to ionization of the N2 molecule to... [Pg.85]

An example of an El forbidden but "vibronically allowed" transition is provided by the singlet n ==> ti transition of H2CO that was discussed earlier in this section. As detailed there, the ground electronic state has Ai symmetry, and the n ==> 71 state is of 1A2 symmetry, so the El transition integral... [Pg.414]

The peak in the UV VIS spectrum of acetone [(CH3)2C=0] corresponding to the transition appears at 279 nm when hexane is the solvent but shifts to 262 nm in water Which is more polar the ground electronic state or the excited stated... [Pg.586]

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