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High Resolution Laser Induced Fluorescence Spectroscopic Study of RuF Timothy C. Steimle, Wilton L. Virgo Tongmei Ma The 60 th International Symposium.

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Presentation on theme: "High Resolution Laser Induced Fluorescence Spectroscopic Study of RuF Timothy C. Steimle, Wilton L. Virgo Tongmei Ma The 60 th International Symposium."— Presentation transcript:

1 High Resolution Laser Induced Fluorescence Spectroscopic Study of RuF Timothy C. Steimle, Wilton L. Virgo Tongmei Ma The 60 th International Symposium on Molecular Spectroscopy and CoF Funded by: DoE-BES

2 Motivation  Establish trends in bonding; provide test data for theoretical calculations. Diatomics : OXIDESNITRIDES CARBIDES Very few halides!!! -1-  Provide the most fundamental property ― dipole moments  FLUORIDES

3 Spectroscopic history of RuF  RuF -2- and CoF  CoF – None! – Adam et al:[18.8] 3  - X 3  ; medium res. LIF spectra – Ram et al:[10.3] 3  - X 3 , C 3  - X 3 , D 3  - X 3  and G 3  - C 3  ; near-IR FT spectra Conclusion: X 3  is an inverted ground state with the X 3  4 spin-component lying lowest; X 3  4 is fully characterized. – Okabayashi et al:X 3  4 ground state; mm-wave abs. spectra

4 Experimental approach RuF and CoF skimmed mol. beam: Pulse Valve /Ablation Source SF 6 (2%) + Ar Plasma Pulse Valve 355 nm Nd:YAG Pulse Laser Ru or Co Rod -3-

5 Stark plates Optical Stark spectroscopy Near natural line width optical spectroscopy: High- resolution LIF spectrometer -4-

6 Survey scan for Ru/SF 6  products -5-  Today’s talk P(?) Q(?) R(?) Results and Discussion

7 -6- RuF is isovalent with FeF But: Ru + :4d 7 and Fe + :3d 6 4s 1 FeF: 6  -X 6  T 00 ~30300 cm -1 ; 6  -X 6  T 00 ~31000 cm-1 Ab initio calc a. for RuF  X 4  I; r e =2.05 Å (B=0.251 cm -1 ) a Per E. Siegbahn, Theor. Chim. Acta (1993) 86, 219 RuF  X 4  9/2  FeF  X 6  9/2

8 High-resolution spectra of RuF -7- P (?) Q (?) R (?)

9 Fluorine hyperfine splitting -8-

10 Stark Spectra of first Q(?R) branch  Eleven components!  Nine components! -9- F=4 F=5 J=4.5  =4.5!!

11 Stark Spectra of R(?) branch Can’t be resolved  High J ! -10-

12 Possible Cases -11- P-branch R-branch(Low-J), R(4.5) R-branch(High J) 4  11/2 - X 4  9/2 Comb/Diff.  B”  & B’  Reasonable! P Q(4.5) R 4  9/2 - X 4  7/2 Comb/Diff.  B’’  Too large!!! 4  7/2 - X 4  9/2 4  9/2 - X 4  9/2

13 Concluding Remarks for RuF -12-  Two new band systems have been observed for RuF. High-resolution spectra have been recorded for the visible band system and hyperfine splitting can be observed.  4  11/2 - X 4  9/2, B’’=0.285; B’=0.287, consistent with ab initio prediction.  Through stark measurement,  3.6D  One anomalous factor we can’t explain is the missing Q branch.

14 Low-resolution LIF spectra of CoF Q P R [18.8] 3  4 - X 3 

15 High-resolution LIF spectra of CoF: R(4) branch of (0,0) band of the 3  4 - X 3  4 transition -14- [18.8] 3  4, J=5 X 3  4, J=4 Relative Energy Level  F=1  F=0

16 [a] Values taken from Ref.: T. Okabayashi and M. Tanimoto, J. Mol. Spectro., 221, 149 (2003). Parameter X 3  4 [a] [18.8] 3  4 T B D   H   a(Co) a D (Co)   eqQ(Co) b F (F) RMS Molecular Constants for the [18.8] 3  4 of CoF (cm -1 )  (D) error

17  Hyperfine LIF spectra of the transition [18.8] 3  4 - X 3  4 has been recorded field free and in the presence of static electric fields. Both two nuclear spin splittings can be observed. Both excited and ground states have F hyperfine spltting in CoF, which is consistent with in RuF.  The predicted spectra agree quite well with the observed spectra which means that our model system works good.  The hyperfine molecular constants for [18.8] 3  4 state and  of the two states were obtained Concluding Remarks for CoF

18

19 J=4 X34X34 F1=7.5 F1=6.5 F1=5.5 F1=4.5 F1=3.5 F1=2.5 F1=1.5 F1=0.5 F1=7.5 F1=6.5 F1=5.5 F1=4.5 F1=3.5 F1=2.5 F1=1.5 F1=8.5 Two nuclear spin splittings observed in CoF -appendix- 59 Co(I=7/2) J=5 [18.8] 3  4 I F =1/2 F  F=1  F=0


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