Nuclear vibrational wave function

Recall that linear molecules have Ah as the absolute value of the axial component of electronic orbital angular momentum the electronic wave functions are classified as 2,n,A,, ... according to whether A is 0,1,2,3,. Similarly, nuclear vibrational wave functions are classified as... 

Here and X are the electronic and nuclear vibrational wave functions, respectively. To the first order of the nuclear displacement we can expand this transition moment in a series... 

Although it was not necessary for the above development, the CBO and ABO approximations should be briefly reviewed In both approximations the vibronic wave function BO(q, g) is written as a product of an electronic wave function ji(q, g) and a nuclear vibrational wave function x(0- In the CBO), the electronic functions are taken to be independent of g (they are all evaluated at some g0), while in the ABO the ip are evaluated parametrically for each value of g. Thus, the vibronic functions are... 

IT. Total Molecular Wave Functdon TIT. Group Theoretical Considerations TV. Permutational Symmetry of Total Wave Function V. Permutational Symmetry of Nuclear Spin Function VT. Permutational Symmetry of Electronic Wave Function VIT. Permutational Symmetry of Rovibronic and Vibronic Wave Functions VIIT. Permutational Symmetry of Rotational Wave Function IX. Permutational Symmetry of Vibrational Wave Function X. Case Studies Lis and Other Systems... 

We now allow nuclear motion and seek vibrational wave functions corresponding to states i i and tjfg. We assume throughout that the subunits have the same point group symmetry in both oxidation states (M and N), and then it is only necessary to consider explicitly totally symmetric normal coordinates of the two subunits (4, 5). Let us assume that there are two on each... 

It should be noted that (4.28) is only an approximation for the nuclear wave function. The perturbation terms (4.36) will mix into the nuclear wave function small contributions from harmonic-oscillator functions with quantum numbers other than v. These anharmonicity corrections to the vibrational wave function will add further to the probability of transitions with At) > 1. 

In the Born-Oppenheimer approximation, the molecular wave function is the product of electronic and nuclear wave functions see (4.90). We now examine the behavior of if with respect to inversion. We must, however, exercise some care. In finding the nuclear wave functions fa we have used a set of axes fixed in space (except for translation with the molecule). However, in dealing with if el (Sections 1.19 and 1.20) we defined the electronic coordinates with respect to a set of axes fixed in the molecule, with the z axis being the internuclear axis. To find the effect on if of inversion of all nuclear and electronic coordinates, we must use the set of space-fixed axes for both fa and if el. We shall call the space-fixed axes X, Y, and Z, and the molecule-fixed axes x, y, and z. The nuclear wave function of a diatomic molecule has the (approximate) form (4.28) for 2 electronic states, where q=R-Re, and where the angles are defined with respect to space-fixed axes. When we replace each nuclear coordinate in fa by its negative, the internuclear distance R is unaffected, so that the vibrational wave function has even parity. The parity of the spherical harmonic Yj1 is even or odd according to whether J is even or odd (Section 1.17). Thus the parity eigenvalue of fa is (- Yf. 

In Section 5.1, we noted that to a good approximation the nuclear motion of a polyatomic molecule can be separated into translational, vibrational, and rotational motions. If the molecule has N nuclei, then the nuclear wave function is a function of 3/V coordinates. The translational wave function depends on the three coordinates of the molecular center of mass in a space-fixed coordinate system. For a nonlinear molecule, the rotational wave function depends on the three Eulerian angles 9, principal axes a, b, and c with respect to a nonrotating set of axes with origin at the center of mass. For a linear molecule, the rotational quantum number K must be zero, and the wave function (5.68) is a function of 6 and only only two angles are needed to specify the orientation of a linear molecule. Thus the vibrational wave function will depend on 3N — 5 or 3N — 6 coordinates, according to whether the molecule is linear or nonlinear we say there are 3N — 5 or 3N — 6 vibrational degrees of freedom. 

We have used the Born Oppenheimer approximation to factor 4 0/3, I,ma into electronic and nuclear parts and have further assumed that the former are orthogonal to enable us to reduce V. Both wave functions may be approximated by products of electronic, nuclear rotation and vibrational wave functions. The last of these may be factored out at once, and... 

The relevant question regarding secondary IEs on acidity is the extent to which IEs affect the electronic distribution. How can an inductive effect be reconciled with the Born-Oppenheimer approximation Although the potential-energy function and the electronic wave function are independent of nuclear mass, an anharmonic potential leads to different vibrational wave functions for different masses. Averaging over the ground-state wave function leads to different positions for the nuclei and thus averaged electron densities that vary with isotope. This certainly leads to NMR isotope shifts (IEs on chemical shifts), because nuclear shielding is sensitive to electron density.16... 

The theory of multi-oscillator electron transitions developed in the works [1, 2, 5-7] is based on the Born-Oppenheimer s adiabatic approach where the electron and nuclear variables are divided. Therefore, the matrix element describing the transition is a product of the electron and oscillator matrix elements. The oscillator matrix element depends only on overlapping of the initial and final vibration wave functions and does not depend on the electron transition type. The basic assumptions of the adiabatic approach and the approximate oscillator terms of the nuclear subsystem are considered in the following section. Then, in the subsequent sections, it will be shown that many vibrations take part in the transition due to relative change of the vibration system in the initial and final states. This change is defined by the following factors the displacement of the equilibrium positions in the... 

Figure 22 Schematic drawing of nuclear wave functions with 30 (to the left) and 3 (to the right) vibrational quanta. The little dots indicate the vibrational wave function amplitude at the classical turning points of the potentials. Portions of the potential energy curves are shown as thick lines. The horizontal lines indicate the energy of the vibronic (vibrational plus electronic) states.

R jm and Rq" are the equilibrium configurations of the nuclei of the parent molecule (RT) in the electron state m and of the daughter molecule (RHe)+ in the electron state n, respectively. Shown in Fig. 1 are the electron terms and the vibrational wave functions of the parent and the daughter molecules together with the transition nuclear density function... 

The integrand [and consequently the whole matrix element Eq. (20)] is nonzero only in the range of definition of the transition nuclear density function Fnii m0(R). Since at room temperatures the P transition occurs from the lowest vibrational states, the range of definition of the vibrational wave function of the initial state A mv(R — Rj m) is quite narrow. Thus, FnfI,mo(R) must be nonzero near the equilibrium distance of the initial molecule Ro,m. 

Here E,j, is the energy of the initial state and R is the nuclear geometry. The division by 3 in (14) comes from orientational averaging. In this form, calculation of the absorption cross section requires the initial vibrational wave function, the transition dipole moment surface and the excited state potential. The reflection principle can be employed for direct or near direct photodissociation. It is again an approximation where the ground state wave function is reflected off the upper potential curve or surface. Prakash et al and Blake et al. [84-86] have used this theory to calculate isotope effects in N2O photolysis. 

Electronic motion with a typical frequency of 3 x 10 s" (i>= 10 cm ) is much faster than vibrational motion with a typical frequency of 3 x 10 s (v = 10 cm" ). As a result of this, the electric vector of light of frequencies appropriate for electronic excitation oscillates far too fast for the nuclei to follow it faithfully, so the wave function for the nuclear motion is still nearly the same immediately after the transition as before. The vibrational level of the excited state whose vibrational wave function is the most similar to this one has the largest transition moment and yields the most intense transition (is the easiest to reach). As the overlap of the vibrational wave function of a selected vibrational level of the excited state with the vibrational wave function of the initial state decreases, the transition moment into it decreases cf. Equation (1.36). Absorption intensity is proportional to the square of the overlap of the two nuclear wave functions, and drops to zero if they are orthogonal. This statement is known as the Franck-Condon principle (Franck, 1926 Condon, 1928 cf. also Schwartz, 1973) ... 

If the potential governing the nuclear motion is accidentally similar in the initial and final electronic states described by % and respectively, with a minimum at the same equilibrium geometry, the two operators vibO . Q) for these two states as well as their vibrational wave functions are identical. The vibrational wave functions and then are orthonormal. The nonvanishing factors will be and only the 0->0, 1- 1,. . ., ... 

If the nuclear spins are taken into account, the total vibrational wave function according to the Pauli principle becomes similar to function (103) ... 

Another factor of which a nonclassical theory must take account is the quantisation of the internal modes of D and A, and the consequent relaxation of the Bom-Oppenheimer constraint that the electron must transfer within a fixed nuclear framework. In classical theory, the vibrational modes of D and A are treated as classical harmonic oscillators, but in reality their quantisation is usually significant (that is, one or more of the vibration frequencies v is sufficiently high that the classical limit hv IcT does not apply). Electron transfer then requires the overlap, not only of the electronic wavefunctions of R and P, but also of their vibrational wavefunctions. It is then possible that nuclear tunnelling may assist electron transfer. As shown in Fig. 4.12, the vibrational wave-functions of R and P extend beyond the classical parabolas and overlap to some extent. This permits nuclear tunnelling from the R to the P surface, particularly in the region just below the classical intersection point. Part of the reorganisation of D and A, required prior to ET in the classical picture, may then occur simultaneously withET, by the nuclei tunnelling short (typically < 0.1 A) distances from their R to their P positions. 

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