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FTIR and DFT Study of the Vibrational Spectrum of SiC 5 Trapped in Solid Ar T.H. Le, C.M.L. Rittby and W.R.M. Graham Department of Physics and Astronomy.

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Presentation on theme: "FTIR and DFT Study of the Vibrational Spectrum of SiC 5 Trapped in Solid Ar T.H. Le, C.M.L. Rittby and W.R.M. Graham Department of Physics and Astronomy."— Presentation transcript:

1 FTIR and DFT Study of the Vibrational Spectrum of SiC 5 Trapped in Solid Ar T.H. Le, C.M.L. Rittby and W.R.M. Graham Department of Physics and Astronomy Molecular Physics Lab Texas Christian University, Fort Worth, TX 67 th International Symposium on Molecular Spectroscopy The Ohio State University June 20, 2012

2 2 Previous research McCarthy et al. (2000) –SiC 5 made using silane and diacetylene –Rotational spectrum detected using microwave spectroscopy Le and Graham (Columbus 2011) –Identified ν 4 ( σ ) mode at 936.9 ± 0.2 cm −1. –Confirmed a linear structure

3 3 Predicted modes of SiC 5 Vibrational mode MPW1PW91/ 6-311+G(3df) DFT (cm -1 ) Infrared intensity (km/mol) ν1(σ)ν1(σ) 2130278 ν2(σ)ν2(σ) 1979617 ν3(σ)ν3(σ) 156110 ν4(σ)ν4(σ) 97732 ν5(σ)ν5(σ) 6161 ν6(π)ν6(π) 50616 9 × Int( ν 4 ) 20 × Int( ν 4 )

4 Laser ablation and matrix isolation Laser ablate rods with 30% Si Trap molecular vapor on a gold mirror at < 20 K Record FTIR spectra on BOMEM DA3 from 400 - 3000 cm -1 at 0.2 cm -1 resolution. 4 Direction of Ar flow FTIR (MCT detector) Mirror Nd:YAG 1064 nm pulsed laser Rod Quartz window CsI window Isotopic shift data Rods enriched with 10% 13 C 29 Si (4.7%) and 30 Si (3.1%) occur in natural abundance.

5 Unidentified C n Frequency (cm -1 ) Absorbance sintered 5% Si / 95% 12 C rod 936.9 935.2 933.5 MPW1PW91/6-311+G(3df) 920 925 930 935 940 ν 4 candidate: 29,30 Si isotopic shifts 30-12-12-12-12-12 28-12-12-12-12-12 29-12-12-12-12-12 5

6 936.9 926.3 926.9 928.9 933.6 934.5 6 920 925 930 935 940 Frequency (cm -1 ) Absorbance sintered 5% Si / 10% C 13 rod CnCn 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12 28-12-12-12-12-12 ν 4 candidate: 13 C isotopic shifts MPW1PW91/ 6-311+G(3df)

7 7 ν 4 : predicted vs observed shifts a MPW1PW91 calculation scaled by a factor of 936.9/977.2. IsotopomerObserved MPW1PW91/ 6-311+G(3df) Scaled a Difference Si-C-C-C-C-C ν obs (cm -1 ) ν DFT (cm -1 ) ν scaled (cm -1 ) Δ ν (cm -1 ) 28-12-12-12-12-12 936.9977.2936.9—— 29-12-12-12-12-12 935.2975.3935.1-0.1 30-12-12-12-12-12 933.5973.3933.2-0.3 28-12-12-12-12-13 934.5975.8935.61.0 28-13-12-12-12-12 933.6975.2935.01.4 28-12-12-12-13-12 928.9967.2927.3-1.6 28-12-13-12-12-12 926.9966.5926.6-0.3 28-12-12-13-12-12 926.3965.7925.9-0.5

8 8 Predicted modes of SiC 5 Vibrational mode MPW1PW91/ 6-311+G(3df) DFT (cm -1 ) Infrared intensity (km/mol) ν1(σ)ν1(σ) 2130278 ν2(σ)ν2(σ) 1979617 ν3(σ)ν3(σ) 156110 ν4(σ)ν4(σ) 97732 ν5(σ)ν5(σ) 6161 ν6(π)ν6(π) 50616 20 × Int( ν 4 )

9 9 30% Si / 10% 13 C rod, LP = 2.5W 1960 1965 1970 1975 1980 1985 1990 1995 C3C3 C3C3 CnCn C9C9 ν 2 candidate: isolating 13 C shifts 1992.9 consistently appears when 936.9 cm -1 appears and with ~ 13 × Int( ν 4 ) 1991.2 1992.9 30% Si / 10% 13 C rod, LP= 3 to 4W

10 10 1960 1965 1970 1975 1980 1985 1990 1995 C3C3 C3C3 CnCn C9C9 overlapped 1986.2 1978.9 1967.2 1959.8 overlapped ν 2 candidate: 13 C shift comparisons 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12 28-12-12-12-12-12 1990.81985.3 1977.8 1966.7 1959.2 1991.2 1992.9 MPW1PW91/6-311+G(3df) 30% Si / 10% 13 C rod

11 11 ν 2 : Predicted vs observed single substitutions shifts a MPW1PW91 calculation scaled by a factor of 1992.9/1978.5. IsotopomerObserved MPW1PW91/6- 311+G(3df) Scaled a Difference Si-C-C-C-C-C ν obs (cm -1 ) ν DFT (cm -1 ) ν scaled (cm -1 )Δ ν (cm -1 ) 28-12-12-12-12-121992.91978.51992.9… 28-12-12-12-12-13 overlapped (1991.2) 1976.41990.8… 28-13-12-12-12-121986.81971.01985.3-1.5 28-12-12-12-13-121978.91963.51977.8-1.1 28-12-13-12-12-121967.21952.51966.7-0.5 28-12-12-13-12-12 overlapped (1959.8) 1945.01959.2…

12 MPW1PW91/6-311+G(3df) ν 2 candidate: double substitutions 30% Si / 10% C 13 rod 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12 1992.9 1991.2 C3C3 C3C3 CnCn C9C9 SiC 3 SiC6C6 C6C6 C6C6 1970 1980 1990 1940 1950 1960 12

13 MPW1PW91/6-311+G(3df) ν 2 candidate: double substitutions 30% Si / 10% C 13 rod 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12 1992.9 1991.2 C3C3 C3C3 CnCn C9C9 SiC 3 SiC6C6 C6C6 C6C6 1970 1980 1990 1940 1950 1960 13

14 14 Isotopomer Observed ν obs MPW1PW91/ 6-311+G(3df) Scaled a ν scaled Difference ∆ν Si-C-C-C-C-C (cm -1 )ν DFT (cm -1 ) (cm -1 ) 28-12-12-12-12-121992.91978.51992.9… 28-12-12-13-12-12overlapped1976.41990.8… 28-13-12-12-12-121978.91963.51977.8-1.1 28-12-12-12-12-131982.71971.01985.32.6 28-12-13-12-12-121967.21952.51966.7-0.5 28-12-12-12-13-12overlapped1945.91960.1… 28-12-12-13-12-131982.71968.01982.3-0.4 28-13-12-13-12-12overlapped1962.41976.7… 28-13-12-12-12-131968.11955.41969.61.5 28-12-13-12-12-131960.91945.61959.8-1.1 28-12-12-13-13-121956.81941.01955.1-1.7 28-12-12-12-13-13overlapped1939.21953.3… 28-13-13-12-12-121948.71934.91949.00.3 28-13-12-12-13-12overlapped1932.31946.4… 28-12-13-12-13-121939.81927.21941.21.4 a MPW1PW91 calculation scaled by a factor of 1992.9/1978.5. ν 2 : Predicted vs observed tentative double substitutions shifts

15 15 Predicted modes of SiC 5 Vibrational mode MPW1PW91/ 6-311+G(3df) DFT (cm -1 ) Infrared intensity (km/mol) ν1(σ)ν1(σ) 2130278 ν2(σ)ν2(σ) 1979617 ν3(σ)ν3(σ) 156110 ν4(σ)ν4(σ) 97732 ν5(σ)ν5(σ) 6161 ν6(π)ν6(π) 50616 9 × Int( ν 4 )

16 16 2005 2010 2015 2020 2025 2030 2035 2040 2045 2045.0 consistently appears when 936.9 cm -1 appears and with ~ 10 × Int( ν 4 ) 2045.0 ν 1 candidate: isolating 13 C shifts C3C3 C3C3 C3C3 soft 30% Si / 10% 13 C rod2021.2

17 17 2005 2010 2015 2020 2025 2030 2035 2040 2045 2045.0 2021.2 ν 1 candidate: 13 C shift comparisons C3C3 C3C3 C3C3 appears related to 2021.2 cm -1 MPW1PW91/6-311+G(3df) soft 30% Si / 10% 13 C rod 2043.12041.52033.02023.7 2011.6

18 18 2005 2010 2015 2020 2025 2030 2035 2040 2045 soft 30% Si / 10% 13 C rod MPW1PW91/6-311+G(3df) 2045.0 2021.2 C3C3 C3C3 C3C3 appears related to 2021.2 cm -1 2042.8 2033.2 2024.0 2012.7 overlapped ν 1 candidate: 13 C shift comparisons 2043.12041.52033.02023.7 2011.6

19 19 2005 2010 2015 2020 2025 2030 2035 2040 2045 soft 30% Si / 10% 13 C rod MPW1PW91/6-311+G(3df) 2045.0 2021.2 C3C3 C3C3 C3C3 appears related to 2021.2 cm -1 2043.12041.52033.02023.7 2011.6 2042.8 2033.2 2024.0 2012.7 overlapped 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12 28-12-12-12-12-12 ν 1 candidate: 13 C shift comparisons

20 20 Isotopomer Observed ν obs MPW1PW91/ 6-311+G(3df) Scaled a ν scaled Difference Δν Si-C-C-C-C-C(cm -1 )ν DFT (cm -1 ) (cm -1 ) 28-12-12-12-12-12 2045.02130.02045.0… 28-12-12-12-12-13 overlapped (2045.0) 2128.02043.1… 28-13-12-12-12-12 2042.82126.42041.5-1.3 28-12-12-12-13-12 2033.22117.52033.0-0.2 28-12-13-12-12-12 overlapped (2024.0) 2107.82023.7… 28-12-12-13-12-12 overlapped (2012.7) 2095.22011.6… a S caled by a factor of 2045.0/2130.0. ν 1 : Predicted vs observed single shifts

21 21 MPW1PW91/6-311+G(3df) 1991.21992.9 C3C3 1990 2000 2010 2020 2030 2040 ν 1 candidate: 2x substitutions soft 30% Si / 10% C 13 rod C3C3 C3C3 C 12 C9C9 CnCn 2045.0 2021.2 28-12-12-12-12-13 28-13-12-12-12-12 28-12-13-12-12-12 28-12-12-13-12-12 28-12-12-12-13-12

22 22 Isotopomer Observed ν obs MPW1PW91/ 6-311+G(3df) Scaled a ν scaled Difference ∆ ν Si-C-C-C-C-C (cm -1 ) ν DFT (cm -1 )(cm -1 ) 28-12-12-12-12-122045.02130.02045.0… 28-12-12-12-12-13overlapped2128.02043.1… 28-13-12-12-12-122042.82126.42041.5-1.3 28-12-12-12-13-122033.22117.52033.0-0.2 28-12-13-12-12-12overlapped2107.82023.7… 28-12-12-13-12-12overlapped2095.22011.6… 28-13-12-12-12-132039.72125.02040.20.5 28-12-12-12-13-13overlapped2117.12032.6… 28-13-12-12-13-122029.62112.32028.0-1.6 28-13-13-12-12-122022.72106.02022.0-0.6 28-12-13-12-12-13overlapped2105.72021.7… 28-12-12-13-12-132009.52094.22010.61.1 28-13-12-13-12-1220072090.02006.6-0.4 28-12-13-12-13-122005.72089.12005.7-0.6 28-12-12-13-13-122002.52084.92001.7-0.8 28-12-13-13-12-12overlapped2070.61988.0… a Results of the MPW1PW91 calculation scaled by a factor of 2045.0/2130.0. ν 1 : predicted vs tentatively identified double substitutions shifts

23 23 1992.9 and 2045 cm -1 do not belong to other linear SiC n Only linear SiC 3, SiC 6 and SiC 8 remain unidentified for SiC n (n < 9) SiC 3 and SiC 8 –Isotopic shift spectra don’t match SiC 6 –Ruled out because the strongest mode DFT predicts, ν 1 ∼ 2224 cm -1, is ∼ 180 cm -1 from observed 2045.0 cm -1 band.

24 24 Conclusions Based upon the observed and DFT predicted relative intensities isotopic shifts identifications are proposed for 3 asymmetric C-C stretch fundamentals of SiC 5 : ● ν 1 ( σ ) = 2045.0 cm −1 ν 4 ( σ ) = 936.9 ● ν 2 ( σ ) = 1992.9

25 25 Acknowledgements TCU Research and Creative Activities Fund The Graduate Student Travel Grant Program W.M. Keck Foundation

26 Questions? 26

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