Presentation is loading. Please wait.

Presentation is loading. Please wait.

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.

Published byJaron Bane Modified over 10 years ago

Similar presentations

Presentation on theme: "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."— Presentation transcript:

1 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 of Physics and Astronomy Texas Christian University Fort Worth, TX 76129 61 st Meeting of the International Symposium on Molecular Spectroscopy The Ohio State University June 19-23, 2006

2 Motivation Astrophysical –Metals observed in small molecules found in circumstellar shells and in the ISM CrO in M stars (Davis, ApJ, 1947) AlNC, NaCl in IRC+10216 (Cernicharo, A&A, 1987; Ziurys, ApJ, 2002) NaCN, MgNC in CRL 2688 (Highberger, ApJ, 2001) –Pure carbon chains observed in circumstellar shells (e.g. C 3, C 5 ) (Hinkle, Science, 1988; Cernicharo, ApJ, 2000; Bernath, Science, 1989) –Silicon-bearing species observed in IRC+10216 include SiCN and SiC 3 (Apponi, ApJ, 1999; Guélin, A&A, 2000) –See WH10 on TiC 3 (Kinzer, Astronomical Species and Processes)

3 Metallocarbohedrenes –Small metal carbon clusters important in understanding the formation of metcars (Guo, Science, 1992; Guo & Castleman, Advances in Metal and Semiconductor Clusters, 1994; Castleman, Nano Lett, 2001) –TiC 2, VC 2 as “building blocks” for larger metcars (Castleman, JPC, 1992; Tono, JCP, 2002) Previous photoelectron spectroscopy (PES) and density functional theory (DFT) studies on MC 2 and MC 3 clusters (M=Sc, V, Cr, Mn, Fe, Co, and Ni) (Wang & Li, JCP, 1999; Wang & Li, JCP, 2000) Motivation

4 Uncertain ground state for CrC 3 (Zhai, JCP, 2004) Electronic configuration GeometryEnergy (eV) anion 4B14B1 fanlike (C 2v ) 0.0 a 4Σˉ4Σˉ linear+0.05 neutral 3B13B1 fanlike (C 2v ) 0.0 a 5Π5Π linear+0.30 DFT predictions for the lowest energy isomers of CrC 3 ˉ and CrC 3 a Denotes ground state energy nearly isoenergetic PES spectra Exhibit features consistent with both isomers. Abundance of C 2v isomer increased with hotter source conditions indicating to the authors the linear isomer may be more stable.

5 Research Objectives To measure the vibrational fundamentals and isotopic shifts of metal carbon (MC n ) species produced by Nd:YAG laser ablation and trapped in solid Ar at ~10 K. To identify and determine the structures of the MC n species created by comparing Fourier transform Infrared (FTIR) measurements with DFT predictions.

6 Strategy 13 C isotopic shifts necessary for species and structure determination. Low 13 C enrichment (~10%) limits isotopic shifts to single 13 C isotopomers, which is useful for large C n clusters (n>6). But for small clusters (n<5), using ~50% 13 C enrichment produces all of the 13 C isotopomers.

7 Experimental Procedures Ar Bomem DA3.16 Fourier Transform Spectrometer KBr beam splitter liquid N 2 cooled MCT detector (550-3900 cm -1 ) laser focusing lens Nd:YAG 1064 nm pulsed laser quartz window to pump 10 -7 Torr or better CsI window to pump 10 -3 Torr carbon rod transition metal rod gold mirror ~10 K See previous talk, WG04 (Gonzalez, Matrix/Condensed Phase)

8 1789.5 C 12 C8C8 C7C7 C 11 C 10 C 11 C6C6 C9C9 C3C3 C8C8 C 10 C9C9 C7C7 C5C5 Frequency (cm -1 ) Absorption 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 12 C rod + Cr rod 12 C rod ν3ν3 2164.1 ν4ν4 2127.8 ν5ν5 2078.1 ν6ν6 2074.9 ν5ν5 2071.7 2038.9 ν3ν3 1998.0 ν6ν6 1952.5 ν5ν5 1946.1 ν7ν7 1915.8 ν7ν7 1894.3 ν5ν5 1856.7 ν8ν8 ν9ν9 1818.0 ν9ν9 1710.5

9 Absorption 1720 1730 1740 1750 1760 1770 1780 1790 Frequency (cm -1 ) Cr rod + 15% 13 C rod 1789.5 1746.1 1735.1 1777.8 1779.7 1743.4 1721.8 C 3 ¯ (Szczepanski, JPCA, 1997) Unidentified feature in pure 12 C spectrum CrOCO (Souter, JACS, 1997)

10 Absorption 1720 1730 1740 1750 1760 1770 1780 1790 Frequency (cm -1 ) Cr rod + 15% 13 C rod 1789.5 1777.8 1779.7 1743.4 Three remaining features Linear CrC 3 ? Nominal enrichment: 15% 13 C Observed effective enrichment: 7% (based on other C n species) Three features are consistent with a molecule containing three inequivalent C atoms.

11 Absorption 1720 1730 1740 1750 1760 1770 1780 1790 Frequency (cm -1 ) 1743.4 Cr rod + 30% 13 C rod 1720.6 1733.5 1731.4 1777.8 1779.7 1767.1 Cr rod + 15% 13 C rod 1789.5 1777.8 1779.7 1743.4 Single 13 C isotopic substitutions Double 13 C isotopic substitutions Full 13 C substitution, i.e. Cr 13 C 3

12 Calculations: Linear and C 2v Isomers of CrC 3 DFT (B3LYP/6-311G + 3df) predicted vibrational frequencies and intensities CrC 3 Isomer Vibrational Mode Frequency (cm -1 ) Infrared intensity (km/mol) 5Π5Πν1(σ)ν1(σ)1947329 linearν2(σ)ν2(σ)13472 ν3(σ)ν3(σ)50827 ν4(π)ν4(π)41724 ν5(π)ν5(π)1522 3B13B1 ν1(a1)ν1(a1)1306 a 8 fanlike (C 2v )ν2(a1)ν2(a1)8162 ν3(a1)ν3(a1)54463 ν4(b1)ν4(b1)51411 ν5(b2)ν5(b2)1473~0 ν6(b2)ν6(b2)38149 a Frequencies for fanlike structure initially published by Wang and Li, 2000. (1789.5)

13 Theoretical Calculations Used Gaussian 03 Used density functional theory (DFT) with B3LYP functional and 6-311+G(3df) basis set Calculations performed for linear and C 2v (fan) structures Calculations for C 2v structure vibrational frequencies in good agreement with previous (Wang & Li, JCP, 2000) 13 C isotopic shift frequencies were also calculated for the linear isomer

14 Cr rod + 30% 13 C rod Cr rod + 15% 13 C rod Absorption 1720.6 1743.4 1733.5 1731.4 1789.5 1777.8 1779.7 1767.1 1720 1730 1740 1750 1760 1770 1780 1790 Frequency (cm -1 ) Single 13 C isotopic substitutions DFT simulation 10% 13 C Double 13 C isotopic substitutions

15 Calculations: Isotopic Shift Frequencies for the ν 1 ( σ ) Mode of Linear CrC 3 Comparison of observed vibrational frequencies (cm -1 ) of the ν 1 ( σ ) mode for 13 C -substituted isotopomers of linear CrC 3 with the predictions of B3LYP/6-311G + (3df) calculations IsotopomerObserved B3LYP/ 6-311G+(3df) Scaled a Difference Cr-C-C-C ν obs ν DFT ν sc Δν=ν obs -ν sc 52-12-12-12(A)1789.51947.4…… 52-13-12-12(B)1777.81932.51775.82.0 52-12-13-12(C)1743.41896.81743.00.4 52-12-12-13(D)1779.71938.01780.9-1.2 52-13-13-13(A')1720.61872.41720.60.0 52-12-13-13(B')1733.51888.61735.5-2.0 52-13-12-13(C')1767.11923.81767.8-0.7 52-13-13-12(D')1731.41883.31730.60.8 a DFT calculations scaled by a factor of 1789.5/1947.4=0.91892.

16 Cr rod + 30% 13 C rod Absorption 1720.6 1743.3 1733.5 1731.4 1789.5 1777.8 1779.5 1767.1 1720 1730 1740 1750 1760 1770 1780 1790 Frequency (cm -1 ) DFT simulation 10% 13 C (A') (C) (B') (D') (D) (B) (A) (C') 52-12-12-12 52-13-12-12 52-13-12-13 52-12-12-13 52-13-13-13 52-13-13-12 52-12-13-13 52-12-13-12

17 Conclusions The linear isomer of CrC 3 has been observed. The ν 1 ( σ ) mode is assigned to 1789.5 cm -1. No evidence of the C 2v (“fan”) structure is observed. Four modes are predicted to lie within detector range. The strongest mode at 544 cm -1 is predicted to be ~20% of the intensity of the ν 1 ( σ ) mode of the linear structure and should be observable. Observation of the linear ground state structure is consistent with the thermal behavior in PES experiments.

18 Acknowledgments Our group would like to acknowledge funding from –Welch Foundation –TCU Research and Creative Activities Fund (TCURCAF) –W.M. Keck Foundation Personal funding acknowledgments –Barnett Scholarship –Texas Space Grant Consortium Fellowship (TSGC)

19 References 1.D.N. Davis, Astrophys. J. 106, 28 (1947). 2.J. Cernicharo and M. Gu é lin, Astron. and Astrophys. 183, L10 (1987). 3.L.M. Ziurys, C. Savage, J.L. Highberger, A.J. Apponi, M. Gu é lin, and J. Cernicharo, Astrophys. J. 564, L45 (2002). 4.J.L. Highberger, C.S. Savage, J.H. Bieging, and L.M. Ziurys, Astrophys. J. 562, 790 (2001). 5.A.J. Apponi, M.C. McCarthy, C.A. Gottlieb, and P. Thaddeus, Astrophys. J. 516, L103 (1999). 6.M. Gu é lin, S. Muller, J. Cernicharo, A.J. Apponi, M.C. McCarthy, C.A. Gottlieb, and P. Thaddeus, Astron. and Astrophys. 363, L9 (2000). 7.K.H. Hinkle, J.J. Keady, and P.F. Bernath, Science 241, 1319 (1988). 8.J. Cernicharo, J.R. Goicoechea, and E. Caux, Astrophys. J. 534, L199 (2000). 9.P.F. Bernath, K.H. Hinkle, and J.J. Keady, Science 244, 562 (1989). 10.B.C. Guo, K.P. Kerns, and A.W. Castleman, Jr., Science 255, 1411 (1992).

20 References 11.B.C. Guo and A.W. Castleman, Jr., in Advances in Metal and Semiconductor Clusters, ed. M.A. Duncan (Jai Press, London, 1994), Vol. 2, 137. 12.S.E. Kooi, B.D. Leskiw, and A.W. Castleman, Jr., Nano Letters 1, 113 (2001). 13.S. Wei, B.C. Guo, J. Purnell, S. Buzza, and A.W. Castleman, Jr., J. Phys. Chem. 96, 4166 (1992). 14.K. Tono, A. Terasaki, T. Ohta, and T. Kondow, J. Chem. Phys. 117, 7010 (2002). 15.S.-L. Wang and X. Li, J. Chem. Phys. 112, 3602 (2000). 16.H.-J. Zhai, L.-S. Wang, P. Jena, G. L. Gustev, and C.W. Bauschlicher, Jr., J. Chem. Phys. 120, 8996 (2004). 17.M.E. Jacox, NIST Vibrational and Electronic Energy Levels Database (http://webbook.nist.gov/chemistry)http://webbook.nist.gov/chemistry 18.J. Szczepanski, S. Eckern, C. Chapo, and M. Vala, Chem. Phys. 211, 359 (1996). 19.P.F. Souter and L. Andrews, J. Am. Chem. Soc. 119, 7350 (1997). 20.J. Szczepanski, C. Wehlburg, M. Vala, J. Phys. Chem. A 101, 7039 (1997).

Download ppt "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."

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,

A Deperturbation Method to Aid in the Interpretation of Infrared Isotopic Spectra G. Garcia and C. M. L. Rittby Texas Christian University Fort Worth,
Photoelectron Imaging of Vibrational Autodetachment from Nitromethane Anions Chris L. Adams, Holger Schneider, J. Mathias Weber JILA, University of Colorado,

Photoelectron Imaging of Vibrational Autodetachment from Nitromethane Anions Chris L. Adams, Holger Schneider, J. Mathias Weber JILA, University of Colorado,
FTIR Spectroscopy of Small Titanium-Carbides A Survey and Preliminary Results Robin Kinzer TCU Molecular Physics Laboratory 31 October 2005.

FTIR Spectroscopy of Small Titanium-Carbides A Survey and Preliminary Results Robin Kinzer TCU Molecular Physics Laboratory 31 October 2005.
Trace Element Abundances in Single Presolar SiC Stardust Grains by Synchrotron X-Ray Fluorescence (SXRF) Zhonghu Cai (XOR) Barry Lai (XOR) Steve Sutton.

Trace Element Abundances in Single Presolar SiC Stardust Grains by Synchrotron X-Ray Fluorescence (SXRF) Zhonghu Cai (XOR) Barry Lai (XOR) Steve Sutton.
CHARACTERIZATION of the SiC 3 H - anion N. Inostroza 1, M. L. Senent 1 1 Instituto de Estructura de la Materia, C.S.I.C, Departamento de Astrofísica Molecular.

CHARACTERIZATION of the SiC 3 H - anion N. Inostroza 1, M. L. Senent 1 1 Instituto de Estructura de la Materia, C.S.I.C, Departamento de Astrofísica Molecular.
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.

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.
Ryunosuke Shishido, Asuka Fujii Department of Chemistry, Graduate School of Science, Tohoku University, Japan Jer-Lai Kuo Institute of Atomic and Molecular.

Ryunosuke Shishido, Asuka Fujii Department of Chemistry, Graduate School of Science, Tohoku University, Japan Jer-Lai Kuo Institute of Atomic and Molecular.
ASTRONOMICAL APPLICATIONS OF NEW LINE LISTS FOR CN, C 2 AND THEIR ISOTOPOLOGUES P. F. Bernath Department of Chemistry and Biochemistry, Old Dominion University,

ASTRONOMICAL APPLICATIONS OF NEW LINE LISTS FOR CN, C 2 AND THEIR ISOTOPOLOGUES P. F. Bernath Department of Chemistry and Biochemistry, Old Dominion University,
Infrared Spectroscopy of Doubly-Charged Metal-Water Complexes

Infrared Spectroscopy of Doubly-Charged Metal-Water Complexes
Supersonic Jet Spectroscopy on TiO 2 Millimeter-wave Spectroscopy of Titanium Monoxide and Titanium Dioxide 63 rd International Symposium on Molecular.

Supersonic Jet Spectroscopy on TiO 2 Millimeter-wave Spectroscopy of Titanium Monoxide and Titanium Dioxide 63 rd International Symposium on Molecular.
Structure Determination of Silicon Clusters in the Gas Phase A Vibrational Spectroscopy and DFT Investigation Jonathan T. Lyon, Philipp Gruene, Gerard.

Structure Determination of Silicon Clusters in the Gas Phase A Vibrational Spectroscopy and DFT Investigation Jonathan T. Lyon, Philipp Gruene, Gerard.
IR spectroscopy of first-row transition metal clusters and their complexes with simple molecules FELIX facility, Radboud University Nijmegen, the Netherlands.

IR spectroscopy of first-row transition metal clusters and their complexes with simple molecules FELIX facility, Radboud University Nijmegen, the Netherlands.
Evidence of Radiational Transitions in the Triplet Manifold of Large Molecules Haifeng Xu, Philip Johnson Stony Brook University Trevor Sears Brookhaven.

Evidence of Radiational Transitions in the Triplet Manifold of Large Molecules Haifeng Xu, Philip Johnson Stony Brook University Trevor Sears Brookhaven.
68th International Symposium on Molecular Spectroscopy Ohio State University June 17-21, 2013 Wei-Li Li, Tian Jian, Gary V. Lopez, and Lai-Sheng Wang Department.

68th International Symposium on Molecular Spectroscopy Ohio State University June 17-21, 2013 Wei-Li Li, Tian Jian, Gary V. Lopez, and Lai-Sheng Wang Department.
Electronic spectroscopy of Li(NH 3 ) 4 Nitika Bhalla, Luigi Varriale, Nicola Tonge and Andrew Ellis Department of Chemistry University of Leicester UK.

Electronic spectroscopy of Li(NH 3 ) 4 Nitika Bhalla, Luigi Varriale, Nicola Tonge and Andrew Ellis Department of Chemistry University of Leicester UK.
FTIR EMISSION SPECTROSCOPY AND AB INITIO STUDY OF THE TRANSIENT BO AND HBO MOLECULES 65 th Ohio State University International Symposium on Molecular Spectroscopy.

FTIR EMISSION SPECTROSCOPY AND AB INITIO STUDY OF THE TRANSIENT BO AND HBO MOLECULES 65 th Ohio State University International Symposium on Molecular Spectroscopy.
Pulsed Field Ionization-Zero Electron Kinetic Energy (PFI-ZEKE) Spectroscopy of Sc-C 6 H 5 X(X=F,CH 3,OH) Complexes Changhua Zhang, Serge A. Krasnokutskia.

Pulsed Field Ionization-Zero Electron Kinetic Energy (PFI-ZEKE) Spectroscopy of Sc-C 6 H 5 X(X=F,CH 3,OH) Complexes Changhua Zhang, Serge A. Krasnokutskia.
62 nd International Symposium on Molecular Spectroscopy June 18-22, 2007 The Pure Rotational Spectra of FeCN (X 6  i ) and FeNC (X 6  i ): It Had to.

62 nd International Symposium on Molecular Spectroscopy June 18-22, 2007 The Pure Rotational Spectra of FeCN (X 6  i ) and FeNC (X 6  i ): It Had to.
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.

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.
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.

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.

Similar presentations

Ads by Google