Ground dipole moments

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... 

C3.4.13)). The dimer has a common ground state and excitation may temrinate in eitlier tire or excited state (see tire solid arrows in figure C3.4.3). The transition dipole moments of tliese transitions are defined as ... 

From a quantum mechanical perspective, an atom or molecule would be considered to have no permanent dipole moment if the probability of finding electrons is symmetric about the nucleus. For example the probability of finding the electron in the ground state of hydrogen is constant with respect to its solid... 

Let (Xgr and jXex be the dipole moments of the ground and excited states. Then if iXgr > the less polar excited state is surrounded by a solvation shell... 

They also noted a strong solvent dependence in the lowest energy band, which corresponds to the lowest excited state of this molecule. This suggests that the dipole moment will change sign as the molecule moves from its ground state to the first excited state. 

Perform a Cl-Singles study of this system, and compare your excited state results with this experimental data. In addition, calculate the dipole moment for the ground and first excited state. 

Compare the dipole moment and the electrostatic potential map for the ground state of acetone to those of the n to pistar state of acetone. Which molecule is more polar Rationalize the differences by appealing to the shape of the orbitals (in ground-state acetone) whose electron populations are changed by excitation. 

Ground to excited state Transition electric dipole moments (Au) ... 

Greater reactivity gamma to an azine-nitrogen would be expected on the basis of the greater ara-quinoid than orf/io-quinoid interactions between various substituents and azine-nitrogens in ground states and excited states. Such a difference in interaction is supported by several kinds of data spectral,basicity, dipole moment, and chlorine quadrupole resonance of halo, methoxy,... 

In 1882 Baeyer and Oekonomides advanced formula 72 (R = H) for isatin on chemical grounds, but shortly thereafter the dioxo structure 73 (R H) was proposed since the ultraviolet spectrum of isatin resembled that of the N—Me derivative (73, R Me) and not that of the O—Me derivative (72, R = Me). " It was later shown, despite a conflicting report, that the ultraviolet spectrum of isatin is very similar to the spectra of both the O— and N—Me deriva-tives - the early investigators had failed to take into consideration the facile decomposition of the O—Me derivative. Although isolation of the separate tautomers of isatin has been reported, - these claims were disproved. A first attempt to determine the position of the mobile hydrogen atom using X-ray crystallographic techniques was inconclusive, but later X-ray work," dipole moment data, and especially the infrared spectrum demonstrated the correctness of the... 

The above results indicate that the selcelion rules are relaxed when the geometry modifications taking place upon pholoexcitalion are considered. Although the transition dipole moment between the ground state and the lowest excited state remains small, the luminescence is no longer entirely quenched by the interchain in-... 

The charge distribution of neutral polar molecules is characterized by a dipole moment which is defined classically by jx = E, , , where the molecular charge distribution is defined in terms of the residual charges (qt) at the position r,. The observed molecular dipole moment provides useful information about the charge distribution of the ground state and its ionic character. 

The observed value of the electric dipole moment of the molecule is 0.297 D, which corresponds to 0.24 D for the moment of the bond. The value of tr, 6.67 D, leads to 3.60% as the contribution of each of the two structures of type 6 to the ground state of the molecule. The ionic character corresponding to Ax = 0.5 is 6.06% from Equation 1-1, which gives bond moment 0.41 D, which would lie close to the straight line in Figure 1-3. 

The properties of excited states are not easy to measure because of their generally short lifetimes and low concentrations, but enough work has been done for us to know that they often differ from the ground state in geometry, dipole moment, and acid or base strength. For example, acetylene, which is linear in the ground state, has a trans geometry... 

The potential energy curves (Fig. 1), the non-adiabatic coupling, transition dipole moments and other system parameters are same as those used in our previous work (18,19,23,27). The excited states 1 B(0 ) and 2 B( rio) are non-adiabatically coupled and their potential energy curves cross at R = 6.08 a.u. The ground 0 X( Eo) state is optically coupled to both the and the 2 R( nJ) states with the transition dipole moment /ioi = 0.25/xo2-The results to be presented are for the cw field e(t) = A Yll=o cos (w - u pfi)t described earlier. However, for IBr, we have shown (18) that similar selectivity and yield may be obtained using Gaussian pulses too. 

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