Bohr orbits

The atomic unit (AU) of dipole moment is that of a proton and electron separated by a distance equal to the first Bohr orbit, oq. Similarly, the au of polarizability is Oq [125]. Express and o for NH3 using both the cgs/esu and SI approach. 

Solution of the Schrodinger equation for R i r), known as the radial wave functions since they are functions only of r, follows a well-known mathematical procedure to produce the solutions known as the associated Laguerre functions, of which a few are given in Table 1.2. The radius of the Bohr orbit for n = 1 is given by... 

It is now known that the view of electrons in individual well-defined quantum states represents an approximation. The new quantum mechanics formulated in 1926 shows unambiguously that this model is strictly incorrect. The field of chemistry continues to adhere to the model, however. Pauli s scheme and the view that each electron is in a stationary state are the basis of the current approach to chemistry teaching and the electronic account of the periodic table. The fact that Pauli unwittingly contributed to the retention of the orbital model, albeit in modified form, is somewhat paradoxical in view of his frequent criticism of the older Bohr orbits model. For example Pauli writes,... 

Thus, for the hydrogen atom (Z = 1) the most probable distance of the electron from the nucleus is equal to the radius of the first Bohr orbit. 

The effect of the spin-orbit interaction term on the total energy is easily shown to be small. The angular momenta L and S are each on the order of h and the distance r is of the order of the radius ao of the first Bohr orbit. If we also neglect the small difference between the electronic mass We and the reduced mass the spin-orbit energy is of the order of... 

What is the velocity of the electron in the first Bohr orbit ... 

According to De Broglie an electron in a Bohr orbit is associated with a standing wave. To avoid self destruction by interference an integral number of wavelengts are required to span the orbit of radius r, which implies n — 2nr, or nh/2n = pr, which is the Bohr condition. As a physical argument the wave conjecture is less plausible, but not indefensible. One possible interpretation considers the superposition of several waves rather than a single monochromatic wave to simulate the behaviour of a particle. 

The differences between Bohr orbits and wave mechanical orbitals are given below. 

Orbits and orbitals are similar in that the radii of Bohr orbits correspond to the distance from the nucleus in an orbital at which the electron is found with high probability. 

Figure 2.1 Electronic orbitals and the resulting emission spectrum in the hydrogen atom, (a) Bohr orbitals of the hydrogen atom and the resulting spectral series, (b) emission spectrum of atomic hydrogen. The spectrum in (b) is calibrated in terms of wavenumber (P), which is reciprocal wavelength. The Balmer series, which consists of those transitions terminating on the second orbital, give rise to emission lines in the visible region of the spectrum. ( 1990 John Wiley Sons, Inc. Reprinted from Brady, 1990, by permission of the publisher.)...

Bohr s hydrogen atom model of 1913 had provided inspiration to a few physicists, like Kossel, who were interested in chemical problems but to very few chemists concerned with the explanation of valence. First of all, the Bohr atom had a dynamic character that was not consistent with the static and stable characteristics of ordinary molecules. Second, Bohr s approach, as amended by Kossel, could not even account for the fundamental tetrahedral structure of organic molecules because it was based on a planar atomic model. Nor could it account for "homopolar" or covalent bonds, because the radii of the Bohr orbits were calculated on the basis of a Coulombic force model. Although Bohr discussed H2, HC1, H20, and CH4, physicists and physical chemists mainly took up the problem of H2, which seemed most amenable to further treatment. 11... 

DSO term is very small. However, as we will see latter, the DSO contribution is significant for certain coupling constants and cannot be discarded. Note that our criterion to estimate the order of magnitude of the individual terms is based on an electron in a Bohr orbit of the hydrogen atom. On some occasions this estimate may not give a good indication of the actual magnitude. 

Electronic and nuclear energy in H2. a. Values for non-interacling electrons. 6, Coulomb energy of nuclear repulsion, c, Approximate electronic energy curve for interacting electrons. Units ordinates, 1 = Rydberg constant, abscissas, 1 = radius of first Bohr orbit in hydrogen atom. 

The atomic unit of length is the radius of the first Bohr orbit in the hydrogen atom when the reduced mass of the electron is replaoed by the rest mass tne. Thus the atomic unit of length is... 

In Figure 2-4 there are shown drawings of the Bohr orbits for hydrogen in the excited states with n = 2, n = 3, and n = 4, with the angular momentum taken equal to + 1 )h/2ir, as required by quantum... 

Fig. 2-4.—Bohr orbits for the hydrogen atom, total quantum number 2, 3, and 4. These orbits are represented as having the values of angular momentum given by quantum mechanics.

These two equations are easily solved. It is found that the radius of the circular Bohr orbit for quantum number n is equal to W/4xaZnt. This can be written as n ao/Zy in which a0 has the value 0.530 A. The speed of the electron in its orbit is found to be v = 2irZe2/nh. For the normal hydrogen atom, with Z = 1 and n = 1, this speed is 2.18 X 108 cm/sec, about 0.7 percent that of the speed of light. 

In the above calculation the system has been treated as though the nucleus were stationary and the electron moved in a circular orbit about the nucleus. The correct application of Newton s laws of motion to the problem of two particles with inverse-square force of attraction leads to the result that both particles move about their center of mass. The center of mass is the point on the line between the centers of the two particles such that the two radii are inversely proportional to the masses of the two particles. The equations for the Bohr orbits with consideration of motion of the nucleus are the same as those given above, except that the mass of the electron, m, is to be replaced by the reduced mass of the two particles, /, defined by the expression 1/m = 1/m + 1/M, where M is the mass of the nucleus. 

The dimensions of the polarizability a are those of volume. The polarizability of a metallic Bphere is equal to the volume of the sphere, and we may anticipate that the polarizabilities of atoms and ions will be roughly equal to the atomic or molecular volumes. The polarizability of the normal hydrogen atom is found by an accurate quantum-mechanical calculation to be 4.5 ao that is, very nearly the volume of a sphere with radius equal to the Bohr-orbit radius a0 (4.19 a ). 

In a classical Bohr orbit, the electron makes a complete journey in 0.15 fs. In reactions, the chemical transformation involves the separation of nuclei at velocities much slower than that of the electron. For a velocity 105 cm/s and a distance change of 10 8 cm (1 A), the time scale is 100 fs. This is a key concept in the ability of femtochemistry to expose the elementary motions as they actually occur. The classical picture has been verified by quantum calculations. Furthermore, as the deBroglie wavelength is on the atomic scale, we can speak of the coherent motion of a single-molecule trajectory and not of an ensemble-averaged phenomenon. Unlike kinetics, studies of dynamics require such coherence, a concept we have been involved with for some time. 

Electric field Field at the first Bohr orbit 5.14 x 109 V/cm... 

If the relativistic effects are sufficiently large and therefore cannot be accounted for as corrections, then as a rule one has to utilize relativistic wave functions and the relativistic Hamiltonian, usually in the form of the so-called relativistic Breit operator. In the case of an N-electron atom the latter may be written as follows (in atomic units, in which the absolute value of electron charge e, its mass m and Planck constant h are equal to one, whereas the unit of length is equal to the radius of the first Bohr orbit of the hydrogen atom) ... 

---