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.

Slides:

Advertisements

Similar presentations

A Deperturbation Method to Aid in the Interpretation of Infrared Isotopic Spectra G. Garcia and C. M. L. Rittby Texas Christian University Fort Worth,

Advertisements

FTIR Isotopic and DFT Studies of Transition Metal-Carbon Clusters Condensed in Solid Argon: CrC 3 S.A. Bates, C.M.L. Rittby, and W.R.M. Graham Department.

FTIR Spectroscopy of Small Titanium-Carbides A Survey and Preliminary Results Robin Kinzer TCU Molecular Physics Laboratory 31 October 2005.

CYCLOPROPYLACETYLENE STUDIED IN COLD FREE JET EXPANSION, ROOM TEMPERATURE GAS, AND DILUTE SOLUTION: TIER MODEL IVR PAM L. CRUM, GORDON G. BROWN, KEVIN.

Rotationally-resolved infrared spectroscopy of the polycyclic aromatic hydrocarbon pyrene (C 16 H 10 ) using a quantum cascade laser- based cavity ringdown.

Observation of the Infrared Spectrum of SiC 5 T. H. Le and W. R. M. Graham Molecular Physics Lab Texas Christian University 66 th International Symposium.

Infrared Spectroscopy of Doubly-Charged Metal-Water Complexes

Systematics in the IR Absorptions of Odd Carbon Chains 21 st of June 2005, Columbus Dmitry Strelnikov, Roman Reusch and Wolfgang Krätschmer Max-Planck-Institut.

 PART Requirements for Spectroscopic Techniques for Polymers 1. High resolution 2. High sensitivity (>1%) 3. High selectivity between molecular.

INFRARED SPECTROSCOPIC STUDY ON FERMI RESONANCE OF THE EXCESS PROTON VIBRATION IN BINARY CLUSTERS Ryunosuke SHISHIDO, Asuka FUJII Department of Chemistry,

Supersonic Jet Spectroscopy on TiO 2 Millimeter-wave Spectroscopy of Titanium Monoxide and Titanium Dioxide 63 rd International Symposium on Molecular.

Terrance J. Codd*, John Stanton†, and Terry A. Miller* * The Laser Spectroscopy Facility, Department of Chemistry and Biochemistry The Ohio State University,

Rovibronic Analysis of the State of the NO 3 Radical Henry Tran, Terrance J. Codd, Dmitry Melnik, Mourad Roudjane, and Terry A. Miller Laser Spectroscopy.

Anh T. Le and Timothy C. Steimle The electric dipole moment of Iridium monosilicide, IrSi Department of Chemistry and Biochemistry, Arizona State University,

FTIR Spectroscopy of the n4 bands of 14NO3 and 15NO3

In-situ Photolysis of Methyl Iodide in Solid Para-hydrogen and Solid Ortho-deuterium Yuki Miyamoto 1, Mizuho Fushitani 2, Hiromichi Hoshina 3, and Takamasa.

Maria Eugenia Sanz, Carlos Cabezas, Santiago Mata, José L. Alonso The Rotational Spectrum of Tryptophan.

FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF ALKALI METAL HYDROSULFIDES: DETECTION OF KSH P. M. SHERIDAN, M. K. L. BINNS, J. P. YOUNG Department of Chemistry.

Novel Applications of a Shape Sensitive Detector 2: Double Resonance Amanda Shirar Purdue University Molecular Spectroscopy Symposium June 19, 2008.

Pulsed-jet discharge matrix isolation and computational study of Bromine atom complexes: Br---BrXCH 2 (X=H,Cl,Br) OSU 66 th International Symposium on.

Electronic Spectroscopy of Palladium Dimer (Pd 2 ) 68th OSU International Symposium on Molecular Spectroscopy Yue Qian, Y. W. Ng and A. S-C. Cheung Department.

1 Infrared Spectroscopy of Ammonium Ion MG03: Sub-Doppler Spectroscopy of ND 3 H + Ions in the NH Stretch Mode MG04: Infrared Spectroscopy of Jet-cooled.

Electronic Transitions of Palladium Monoboride and Platinum Monoboride Y.W. Ng, H.F. Pang, Y. S. Wong, Yue Qian, and A. S-C. Cheung Department of Chemistry.

Tunable Infrared Laser Desorption/Ionization Time-of-Flight Mass Spectroscopy of Thin Films Timothy Cheng, Michael Duncan Department of Chemistry, University.

Electronic spectroscopy of CHBr and CDBr Chong Tao, Calvin Mukarakate, Mihaela Deselnicu and Scott A. Reid Department of Chemistry, Marquette University.

SPECTROSCOPY OF AND PHOTOINDUCED ELECTRON TRANSFER IN THE COMPLEXES OF C 2 H 4 WITH I AND I 2 Lisa George, Aimable Kalume, and Scott A. Reid Department.

Rotationally-Resolved Spectroscopy of the Bending Modes of Deuterated Water Dimer JACOB T. STEWART AND BENJAMIN J. MCCALL DEPARTMENT OF CHEMISTRY, UNIVERSITY.

Adrian M. Gardner, Alistair M. Green, Victor M. Tamé-Reyes, Victoria H. K Wilton and Timothy G. Wright Electronic and Photoelectron Spectroscopy of Toluene.

Infrared Spectroscopy & Structures of Mass-Selected Rhodium Carbonyl & Rhodium Dinitrogen Cations Heather L. Abbott, 1 Antonio D. Brathwaite 2 and Michael.

Direct Measurement of Weak Collisions and Collision Rates using High-Resolution Transient IR Absorption Spectroscopy Daniel K. Havey, Qingnan Liu, Amy.

E. Gonzalez, C.M.L. Rittby, and W.R.M. Graham

Infrared Spectra of Chloride- Fluorobenzene Complexes in the Gas Phase: Electrostatics versus Hydrogen Bonding Holger Schneider OSU International Symposium.

65th Ohio State University Symposium on Molecular Spectroscopy June 21–25, 2010 Stark spectrum simulation of X 2 Y 4 asymmetric molecules: application.

First Observation of a Vibrational Fundamental of SiC 6 Si Trapped in Solid Ar T.H. Lê, C.M.L. Rittby and W.R.M. Graham Department of Physics and Astronomy.

70th ISMS Vibration-Rotation Analysis of the 13 CO 2 Asymmetric Stretch Fundamental Band in Ambient Air for the Physical Chemistry Teaching Laboratory.

June 25, th International Symposium on Molecular Spectroscopy Hyperfine Resolved Pure Rotational Spectroscopy of ScN, YN, and BaNH (X 1  + ):

Infrared Observation of the ν 1 (  ) and ν 2 (  ) Stretching Modes of Linear GeC 3 E. Gonzalez, C.M.L. Rittby, and W.R.M. Graham Department of Physics.

Sand in the laboratory. Production and interrogation of gas phase silicates. Damian L Kokkin and Timothy Steimle.

Anomalous CH Stretch Intensity Effects in Halomethyl Radicals: “Charge-Sloshing” vs. Bond- Dipole Contributions to IR Transition Moments E.S. Whitney,

D. Zhao, K.D. Doney, H. Linnartz Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, the Netherlands T he 3 μm Infrared Spectra.

FTS Studies Of The Isotopologues Of CO 2 Toward Creating A Complete And Highly Accurate Reference Standard Ben Elliott, Keeyoon Sung, Charles Miller JPL,

A Missing Link: The Rotational Spectrum, Geometrical Structure, and Astronomical Discovery of Disilicon Carbide, SiCSi M.-A. Martin-Drumel, C. A. Gottlieb,

60th International Symposium on Molecular Spectroscopy

O. PIRALI, J. OOMENS, N. POLFER FOM Rijnhuizen, 3439MN Nieuwegein, The Netherlands Y. UENO, R. MABOUDIAN Department of Chemical Engineering, U.C. Berkeley,

Laser spectroscopy of a halocarbocation: CH 2 I + Chong Tao, Calvin Mukarakate, and Scott A. Reid Department of Chemistry, Marquette University 61 st International.

Sub-Doppler Jet-Cooled Infrared Spectroscopy of ND 2 H 2 + and ND 3 H + in NH Stretch Fundamental Modes Astronomical Molecular Spectroscopy in the Age.

FTIR Observation and DFT Study of CoC 3 Trapped in Solid Ar S.A. Bates, J.A. Rhodes, C.M.L. Rittby, and W.R.M. Graham Department of Physics and Astronomy.

Rotational Spectroscopy of OCS in Superfluid Helium Nanodroplets Paul Raston, Rudolf Lehnig, and Wolfgang Jäger Department of Chemistry, University of.

Conformational effects on resolved emission spectra of floppy aromatic molecules Sujit S. Panja Department of chemistry Indian Institute of Technology.

FTIR AND DFT STUDIES OF THE MgC 3 - ANION IN SOLID Ar M. Bejjani, C. M. L. Rittby, and W. R. M. Graham Department of Physics and Astronomy Texas Christian.

Lineshape analysis of CH3F-(ortho-H2)n absorption spectra in 3000 cm-1 region in solid para-H2 Yuki Miyamoto Graduate School of Natural Science and Technology,

Time-resolved infrared diode laser spectroscopy of the n1 band of CoNO

FTIR Matrix Study of Potential Circumstellar Molecules: TiC3

Andrew J. Wilson and Prashant K. Jain Department of Chemistry

FTIR MATRIX AND DFT STUDY OF THE VIBRATIONAL SPECTRUM OF CYCLIC ScC3

INFRARED SPECTROSCOPY OF DISILICON-CARBIDE, Si2C

The Near-IR Spectrum of CH3D

Jacob T. Stewart and Bradley M

FTIR Matrix and DFT Study of the Vibrational Spectrum of NiC3Ni

Timothy C. Steimle , T. Maa, S. Muscarella, and Damian Kokkin

Tokyo Univ. Science Mitsunori Araki, Yuki Matsushita, Koichi Tsukiyama

Single Vibronic Level (SVL) emission spectroscopy of CHBr: Vibrational structure of the X1A and a3A  states.

Spectroscopic Research of Pt + NH3

HIGH RESOLUTION INFRARED SPECTRA OF TRIACETYLENE*

Molecular Vibrations and IR Spectroscopy

E. D. Pillai, J. Velasquez, P.D. Carnegie, M. A. Duncan

Analytical methods Prepared By Dr. Biswajit Saha.

CHONG TAO, D. BRUSSE, Y. MISHCHENKO, C. MUKARAKATE and S. A. REID,

Fourier Transform Infrared Spectral

Presentation transcript:

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 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 ± 0.2 cm −1. –Confirmed a linear structure

3 Predicted modes of SiC 5 Vibrational mode MPW1PW91/ G(3df) DFT (cm -1 ) Infrared intensity (km/mol) ν1(σ)ν1(σ) ν2(σ)ν2(σ) ν3(σ)ν3(σ) ν4(σ)ν4(σ) ν5(σ)ν5(σ) 6161 ν6(π)ν6(π) × Int( ν 4 ) 20 × Int( ν 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 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.

Unidentified C n Frequency (cm -1 ) Absorbance sintered 5% Si / 95% 12 C rod MPW1PW91/6-311+G(3df) ν 4 candidate: 29,30 Si isotopic shifts

Frequency (cm -1 ) Absorbance sintered 5% Si / 10% C 13 rod CnCn ν 4 candidate: 13 C isotopic shifts MPW1PW91/ G(3df)

7 ν 4 : predicted vs observed shifts a MPW1PW91 calculation scaled by a factor of 936.9/ IsotopomerObserved MPW1PW91/ 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 ) ——

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

9 30% Si / 10% 13 C rod, LP = 2.5W C3C3 C3C3 CnCn C9C9 ν 2 candidate: isolating 13 C shifts consistently appears when cm -1 appears and with ~ 13 × Int( ν 4 ) % Si / 10% 13 C rod, LP= 3 to 4W

C3C3 C3C3 CnCn C9C9 overlapped overlapped ν 2 candidate: 13 C shift comparisons MPW1PW91/6-311+G(3df) 30% Si / 10% 13 C rod

11 ν 2 : Predicted vs observed single substitutions shifts a MPW1PW91 calculation scaled by a factor of / IsotopomerObserved MPW1PW91/ 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 ) … overlapped (1991.2) … overlapped (1959.8) …

MPW1PW91/6-311+G(3df) ν 2 candidate: double substitutions 30% Si / 10% C 13 rod C3C3 C3C3 CnCn C9C9 SiC 3 SiC6C6 C6C6 C6C

MPW1PW91/6-311+G(3df) ν 2 candidate: double substitutions 30% Si / 10% C 13 rod C3C3 C3C3 CnCn C9C9 SiC 3 SiC6C6 C6C6 C6C

14 Isotopomer Observed ν obs MPW1PW91/ G(3df) Scaled a ν scaled Difference ∆ν Si-C-C-C-C-C (cm -1 )ν DFT (cm -1 ) (cm -1 ) … overlapped … overlapped … overlapped … overlapped … overlapped … a MPW1PW91 calculation scaled by a factor of / ν 2 : Predicted vs observed tentative double substitutions shifts

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

consistently appears when cm -1 appears and with ~ 10 × Int( ν 4 ) ν 1 candidate: isolating 13 C shifts C3C3 C3C3 C3C3 soft 30% Si / 10% 13 C rod2021.2

ν 1 candidate: 13 C shift comparisons C3C3 C3C3 C3C3 appears related to cm -1 MPW1PW91/6-311+G(3df) soft 30% Si / 10% 13 C rod

soft 30% Si / 10% 13 C rod MPW1PW91/6-311+G(3df) C3C3 C3C3 C3C3 appears related to cm overlapped ν 1 candidate: 13 C shift comparisons

soft 30% Si / 10% 13 C rod MPW1PW91/6-311+G(3df) C3C3 C3C3 C3C3 appears related to cm overlapped ν 1 candidate: 13 C shift comparisons

20 Isotopomer Observed ν obs MPW1PW91/ G(3df) Scaled a ν scaled Difference Δν Si-C-C-C-C-C(cm -1 )ν DFT (cm -1 ) (cm -1 ) … overlapped (2045.0) … overlapped (2024.0) … overlapped (2012.7) … a S caled by a factor of / ν 1 : Predicted vs observed single shifts

21 MPW1PW91/6-311+G(3df) C3C ν 1 candidate: 2x substitutions soft 30% Si / 10% C 13 rod C3C3 C3C3 C 12 C9C9 CnCn

22 Isotopomer Observed ν obs MPW1PW91/ G(3df) Scaled a ν scaled Difference ∆ ν Si-C-C-C-C-C (cm -1 ) ν DFT (cm -1 )(cm -1 ) … overlapped … overlapped … overlapped … overlapped … overlapped … overlapped … a Results of the MPW1PW91 calculation scaled by a factor of / ν 1 : predicted vs tentatively identified double substitutions shifts

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 cm -1 band.

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 ) = cm −1 ν 4 ( σ ) = ● ν 2 ( σ ) =

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

Questions? 26