Home work Physical and Theoretical Chemistry IV
- Molecular Spectroscopy -

Discussion  Fr 26.06.2009 at 12:15,  PK11-2


Home work 10       Rotational Structure of Electronic Transitions; Photoelectron spectroscopy

 

Exercise 1:       

a)  One of the excited states of Li2 molecule has the valence electron configuration 1σ1g 1p1u .

a.   Calculate the multiplicity (2S+1), parity (g, u), and the projection of the total orbital angular momentum (Λ) of all available molecular terms. Which of these terms has the lowest energy? 

b.      Are these molecular states stable, or unstable? Why?

c.       Assume that these excited states are populated by electric discharge. Can these states be optically detected by observing  fluorescence to the molecular ground state? If yes, what will be the rotational structure of the fluorescence line?

b) Consider the optical electronic transition between the OH ground state  2Π and the first excited state  2Σ .  Which rotational branches contains the UV absorption spectrum of this transition? 

 

Exercise 2:   

a)   Consider the ionization of N2 molecule from the 3σg bonding orbital (HOMO) with synchrotron radiation at λ=50 nm. What will be the expected maximum kinetic energy of photoelectrons  in eV if  the ionization energy of the molecule is Ii =15.59 eV?

b)  What will be the electron kinetic energy if the molecular ion N2+ in the above problem  is produces in its v'=2 vibrational energy state?  The vibrational constant of the molecular ionic state is ωe' = 2207 cm-1.

c)  What will be the maximum kinetic energy of the photoelectrons if  N2 molecule is ionized from the inner 1pu bonding orbital which has 1.1 eV lower energy than the 3σg bonding orbital? 

 

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