Question

what is the effect of breakdown of born Oppenheimer approximation on P and R branches of the IR spectrum of a diatomic molecule answer in 75 word​

Answer 1

Answer:

The Born-Oppenheimer approximation is one of the basic concepts underlying the description of the quantum states of molecules. This approximation makes it possible to separate the motion of the nuclei and the motion of the electrons. This is not a new idea for us. We already made use of this approximation in the particle-in-a-box model when we explained the electronic absorption spectra of cyanine dyes without considering the motion of the nuclei. Then we discussed the translational, rotational and vibrational motion of the nuclei without including the motion of the electrons. In this chapter we will examine more closely the significance and consequences of this important approximation. Note, in this discussion nuclear refers to the atomic nuclei as parts of molecules not to the internal structure of the nucleus.

The Born-Oppenheimer approximation neglects the motion of the atomic nuclei when describing the electrons in a molecule. The physical basis for the Born-Oppenheimer approximation is the fact that the mass of an atomic nucleus in a molecule is much larger than the mass of an electron (more than 1000 times). Because of this difference, the nuclei move much more slowly than the electrons. In addition, due to their opposite charges, there is a mutual attractive force of

Ze2r2(10.1.1)

acting on an atomic nucleus and an electron. This force causes both particles to be accelerated. Since the magnitude of the acceleration is inversely proportional to the mass, a = f/m, the acceleration of the electrons is large and the acceleration of the atomic nuclei is small; the difference is a factor of more than 1000. Consequently, the electrons are moving and responding to forces very quickly, and the nuclei are not. You can imagine running a 100-yard dash against someone whose acceleration is a 1000 times greater than yours. That person could literally run circles around you. So a good approximation is to describe the electronic states of a molecule by thinking that the nuclei aren't moving, i.e. that they are stationary. The nuclei, however, can be stationary at different positions so the electronic wavefunction can depend on the positions of the nuclei even though their motion is neglected.

Now we look at the mathematics to see what is done in solving the Schrödinger equation after making the Born-Oppenheimer approximation. For a diatomic molecule as an example, the Hamiltonian operator is grouped into three terms

Answer 2

Effect of breakdown of Born Oppenheimer approximation

Explanation:

• This approximation is used to understand vibration-rotation spectra.
• It states that since the scales of determining energy are different, the two motions can be treated independently.
• Spectra analysis indicates information about the vibration frequencies, rotational constants and all corresponding parameters.
• However, real spectra analysis shows a crowding of lines at the higher wavenumber R branches and spacing out of P branches.
• this implies that rotational constant is not independent of the vibrational quantum number which implies the breakdown of Born Oppenheimer approximation.