Understanding Energy and Frequency in Rotation Spectra

In summary, the conversation discusses the Hamiltonian for a diatomic molecule, the energy levels and eigenvalues, and the relationship between rotation frequency and energy. The argument presented is about the behavior of low-lying states and the frequency of emitted radiation.
  • #1
unscientific
1,734
13
I don't really understand the explanation given in Binney's text about:

htinb4.png


Hamiltonian is given by:

[tex]H = \frac{\hbar^2}{2} \left( \frac{J_x^2}{I_x} + \frac{J_y^2}{I_y} + \frac{J_z^2}{I_z} \right)[/tex]

Orient axes such that ##I_x = I_y = I##.

[tex]H = \frac{\hbar^2}{2} \left( \frac{J^2}{I} + J_z^2(\frac{1}{I_z} - \frac{1}{I})\right)[/tex]

Energy is given by:

[tex]E_{jm} = \frac{\hbar^2}{2} \left[ \frac{j(j+1)}{I} + m^2(\frac{1}{I_z} - \frac{1}{I}) \right][/tex]

We are only interested in states:

[tex]E_{jm} = \frac{\hbar^2}{2I} j(j+1) [/tex]

Emitted energy and frequency are:

[tex]\Delta E_p =\pm (E_j - E_{j-1}) = \pm j\frac{\hbar^2}{I}[/tex]
[tex]v_j = j\frac{\hbar}{2\pi I}[/tex]
Let's try to analyze the explanation here.

1. Yes, energy, Jz and J2 share the same eigenstates ##|j, m>##.

2. <J2> = j(j+1) : Yes, since that is the eigenvalue and eigenvalue correspond to real observables.

3. Why do low lying states with ##m = 0## and ##j~O(1)## lead to: ## j(j+1) >> j ##? Firstly, doesn't low lying states correspond to a low ##j##? And what does m have to do with anything? ##m## was defined as the eigenvalue of Ji and ##j = m_{max}##

The rest of the argument doesn't make any sense at all..
 
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  • #2
He didn't say j(j+1) >> j. He said "significantly larger".

It would help to know what system this discussion is about, what the upper and lower states are, what νj is, and what is contained in Eq.(7.24).
 
  • #3
Bill_K said:
He didn't say j(j+1) >> j. He said "significantly larger".

It would help to know what system this discussion is about, what the upper and lower states are, what νj is, and what is contained in Eq.(7.24).

It's about the energy levels in rotation spectra of diatomic molecules - specifically CO molecule in this case.

The problem is I'm not sure what he is referring to. This is taken from Binney's book, pg 140:

25tz4hy.png
 
  • #4
Bill_K said:
He didn't say j(j+1) >> j. He said "significantly larger".

Much more importantly, he said larger than ##j^2##, not j.
 
  • #5
DrDu said:
Much more importantly, he said larger than ##j^2##, not j.

Ok besides that, I don't get the rest of the argument about rotation frequencies at all!
 
  • #6
Classically, you have two ways to determine the rotation frequency: Either from the energy of the state using: ##\omega=\sqrt(2IE)## or measuring the frequency of the emitted radiation, ##\omega_\mathrm{transition}##. In QM, the energy is quantized, so ω, as determined from E will depend on J. He is saying ##\omega(j-1)<\omega_\mathrm{transition}<\omega(j)##, where the transition is from j to j-1. In the limit of large j, all thre values will converge to the same classical value.
 

Related to Understanding Energy and Frequency in Rotation Spectra

1. What is rotation spectra?

Rotation spectra is a type of spectroscopy that involves the study of the rotational energy levels of molecules. It provides information about the structural and chemical properties of molecules, such as their bond lengths and moments of inertia.

2. How is rotation spectra measured?

Rotation spectra is typically measured using a technique called microwave spectroscopy. This involves passing microwave radiation through a sample of molecules and analyzing the absorption or emission of specific frequencies, which correspond to the rotational energy levels of the molecules.

3. What factors affect the energies of rotational states?

The energies of rotational states are affected by several factors, including the mass and shape of the molecule, the type and strength of chemical bonds present, and the temperature and pressure of the environment. Changes in these factors can cause shifts in the energy levels and result in changes in the rotation spectra.

4. What is the significance of studying rotation spectra?

Studying rotation spectra is important for understanding the structure and behavior of molecules, which has implications in various fields such as chemistry, physics, and biology. It can also aid in the identification and characterization of unknown substances, as each molecule has a unique rotation spectra that can serve as a fingerprint for identification.

5. How is rotation spectra used in practical applications?

Rotation spectra has a wide range of practical applications, including in the fields of astronomy, atmospheric science, and pharmaceutical research. For example, it is used in the detection and analysis of molecules in interstellar space, the monitoring of atmospheric pollutants, and the development of new drugs and materials.

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