1. LASER Induced Fluorescence of Iodine Eðlisefnafræði 5 – 30. mars 2006 Ómar Freyr Sigurbjörnsson

2. Introduction Iodine is the heaviest common halogen and exists as a solid at room temperature in sublimation equilibrium with its vapor. Its vapor has the appearance of a violet gas, indicating a visible absorption. This absorption corresponds to a spin-forbidden transition from the lowest vibrational levels of the singlet electronic ground state to high vibrational levels of a triplet excited state. B 3   u  X 1  g  By laser excitation, the reverse process of fluorescence is studied

4. The experimental setup

5. Experimental Iodine crystals were inserted inside the fluorescence cell and the cell was then vacuated and heated The monochromator was set to a wavelength of 630 nm and slidt width of 2000  m for the indirect absorption measurement by scanning the Dye-Laser and recording the amount of fluorescence The fluorescence spectra was then recorded by scanning the monochromator 1 nm/min and slit width of 500  m for a fixed Laser excitation wavelength Getting a strong signal was difficult and the slit width could not be smaller, resulting in lower resolution Optimally the scanning speed should be slower

6. Iodine absorption spectrum Generally an absorption spectrum can mostly give us information on the physical characteristics of excited states of molecules Alternatively, emission spectra contain information on the ground state Measuring directly the absorption spectrum of a molecule using Laser light is impractical The light is so strong that almost no difference is detectable due to molecular absorption So the absorption spectrum of Iodine is measured indirectly by measuring the amount of fluorescence as a function of laser wavelength

7. Recorded Iodine fluorescence as a function of Laser wavenumber 588,2 586,5 nm

8. Iodine absorption spectrum Rotational structure is observed due to the vibrational transition v’=16  v’’=2 (B  X) as determined by the UV/VIS absorption spectrum recorded and assigned in an experiment performed in Physical Chemistry 2 Laser wavelength of 17010,3 cm -1 (587,88 nm) is selected to excite iodine molecules to the specific rotational and vibrational state, then the fluorescence to the ground state vibrational levels is recorded

9. Iodine fluorescence spectra The expected Iodine fluorescence spectra should have peaks corresponding to different vibrational levels of the ground state Also, each vibrational peak should be rotationally split in two due to the fact that for each transition, the selection rule  J= ± 1 applies

10. Recorded Iodine fluorescence spectra 633 nm 593 nm

11. Analysis of measured and calculated peak positions A transition between two electronic states is described by the equation (neglecting rotational contribution) (v",v’ ) = el + G(v’) - G(v") v’’+ ½ measured [nm] measured [cm -1 ] calculated [cm -1 ] 3,5593,51685016892 4,5600,71664516682 5,5608,71642916474 6,5615,81623816267 7,5623,91602816061 Where G(v) =  e (v+ ½ ) -  e  e (v + ½ ) 2 By plotting measured against v’’+ ½ the constants  e and  e  e can be determined

12. measured [cm -1 ] Huber & Herzberg [cm -1 ] ee 216,9214,50 eeee 1,070,614 Results

13. Discussion The rotational split mentioned before can be seen in the recorded spectrum shown earlier If the data and resolution are good enough, analysis can be performed to assign the rotational quantum number J’ and rotational constants B for the ground vibrational states The following equation describes the relationship  E(J’,V’’) = 2(2J’+1)B e ’’ -  e ’’ 2(2J’+1)(v’’+ ½) By plotting  E as a function of v’’+ ½ and using known values for B e ’’ &  e ’’, the constant J’+1 can be found and consequently other B values Unfortunately my recorded spectrum does not yield satisfactory results by such treatment

14. Discussion There are a few things that could explain this Problems with signal strength and noise Scan speed and slit width to high Some data points from laser pulses are lost/do not register on the computer so the data aquisition is not completly continous More peaks and more scans are required for a thorough treatment

15. I wish to thank Mr. Wang for his help in performing this experiment