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

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Presentation transcript:

VIBRATIONAL SPECTROSCOPY OF GERMANIUM-CARBON CLUSTERS: ν4(σu) MODE OF GeC5Ge E. Gonzalez, C.M.L. Rittby, and W.R.M. Graham Texas Christian University Molecular Physics Laboratory

Motivation The Group IVB molecular clusters, SinCm, GenCm, and SinCmGel, are of experimental and theoretical interest because of their novel structures and potential applications in semiconductor technology and microelectronics products (J. Karolczak,J. Chem. Phys. (1995), O. Leifeld, Nano. (1999)., O. Leifeld, Appl. Phys. Lett. (1999). ,R. Hartmann, Appl. Phys. Lett. (1998).) . Previously, we have reported vibrational spectra for SinCm (X.D. Ding, J. Chem, Phys. (1999) ) , GenCm , and SinCmGel (D.L. Robbins, J. Chem. Phys. (2001,2002,2004). ) clusters. Could we form new species?

Objectives To form novel germanium-carbon clusters by dual-laser ablation of germanium and carbon rods. Identify structure via isotopic shift measurements and assign the vibrational fundamentals

Dual Laser Ablation Setup laser focusing lenses Nd-YAG 1064 nm pulsed lasers, 1.0 to 3.0 Watts Gold mirror held held at ~10 K Quartz window FTIR (MCT detector) ~10-8Torr CsI window Germanium Carbon Ar flow

Strategy To identify structure: To measure frequencies and intensities of isotopomers formed by evaporating carbon rods with a 13C enrichment. In order to limit the complexity of the isotopic spectrum two experiments are carried out with different carbon rods having low (5-30%) and high (70-95%) 13C enrichment respectively. The first one to obtain single and double 13C substitutions, the second to obtain 12C substitutions.

Strategy (cont.) DFT Calculations: To perform DFT calculations of geometries linked with the obtained spectra. Isotopic shift calculation and simulated spectra with the experimental 13C enrichment are generated to sustain the identified structure and vibrational assignment.

Carbon Rods Homemade carbon rods with the desired ratio of 13C:12C by mass weight. Isotopomers probability of Cn bearing species: : Number of 13C isotopic substitutions : Number of carbon atoms : 13C concentration 12 13

Example: C5 bearing species Single substitutions Example: C5 bearing species Double substitutions Triple substitutions Quadruple substitutions Probability 0.1 Low 13C High 13C 0.08 0.06 0.04 0.02 20 40 60 80 100 13C Concentration

C5 90% 12C / 10% 13C 10% 12C / 90% 13C 12-12-12-12-12 13-13-13-13-13 2130 2140 2150 2160 2080 2090 2100 2110 2120 12-13-13-13-13 13-12-12-12-12 Absorbance 13-12-13-13-13 12-13-12-12-12 13-13-12-13-13 12-12-13-12-12 12C12,v7 Frequency (cm-1)

(a) 12C rod + Ge rod (b) 12C rod C9 n6 GeC9 n4 GeC3Ge n3 GenCm C6 n5 1998.0 n6 GeC9 n4 1928.3 (a) 12C rod + Ge rod GeC3Ge n3 GenCm C6 1952.5 n5 GeC7 n1 2063.8 2093.2 GenCm 1920.3 2158.0 1936.7 Cn C7 n4 2127.8 C5 n3 2164.1 n9 n3 n7 C12 n5 C3 C11 n7 n8 C7 1894.3 1818.0 C10 1946.1 2038.9 C11 Absorbance 1915.8 1856.7 (b) 12C rod 1750 1800 1850 1900 1950 2000 2050 2100 2150

(a) Ge rod and 15% 13C rod C7 C5 Cn 2100 2110 2120 2130 2140 2150 2160 C5 single substitutions C5 double substitutions C7 (A) C5 2127.9 2158.0 2164.1 C12 2140.0 (B) (C),(F) (G) (D),(H) (I) Cn 2155.1 (J) Absorbance (E) 2116.3 2116.8 2138.2 2142.3 2123.4 2105.2 2154.2 Frequency (cm-1) 2100 2110 2120 2130 2140 2150 2160 2170

(a) Ge rod and 85% 13C rod C5 C5 single substitutions 2080.4 (A') C5 single substitutions C5 double substitutions 2074.7 2077.8 (B' ) (C' ),(F' ) (H' ) (I' ) (D') 2098.8 2114.4 2116.6 2120.2 Absorbance Frequency (cm-1) 2070 2080 2090 2100 2110 2120 2130 2140 2150

DFT Calculations We did DFT calculations for GeC5Ge because: It is consistent with the shown isotopic spectra. Previous experimental measurements and DFT calculations have shown that the original linear carbon chain structure is retained on the addition of a Si and Ge atom to one or both end. For example, SiC3Si, SiC4, SiC4Si, GeC3Ge, GeC7, GeC9, GeC3Si.

DFT predicted (B3LYP/cc-pVDZ) ground state geometry for GeC5Ge cluster 1.2918 1.2897 1.7897 1.7897 Å 1.2897 1.2918 Ge

DFT B3LYP/cc-pVDZ predicted vibrational frequencies (cm-1) and band intensities for the linear GeC5Ge 2158.0 2163.9 2140 2160 2180 calculated 4592 km/mol 2539 GeC5Ge C5

Statistical Analysis Molecule Exp. Frq. Theo. Frq Ratio y = 0.9557x + 13.661 R 2 = 0.969 1000.0 1200.0 1400.0 1600.0 1800.0 2000.0 2200.0 2400.0 1500.0 2500.0 Theoretical Frequencies (cm-1) Experimetal Frequencies (cm-1)

Expected Experimental Frequency: (using linear regression) Statistical Analysis Molecule Exp. Frq. Theo. Frq Ratio Theoretical Frequency: 2135.0 cm-1 Expected Experimental Frequency: (2054 ± 133) cm-1 (using linear regression) ] 2187 cm-1 [ 1921 cm-1 2158 cm-1!

Comparison of observed vibrational frequencies (cm-1) of the 4(σu) mode for 13C- substituted isotopomers of linear GeC5Ge with the predictions of B3LYP/cc-pVDZ level calculations. aResults of the DFT-B3LYP/cc-pVDZ calculation scaled by a factor of 2158.0/2135.0=1.01076. bOverlapped by band C. cOverlapped by band D.

(a) Ge rod and 15% 13C rod (b) DFT simulation 15% 13C 2100 2110 2120 2123.4 2127.9 2155.1 2158.0 2164.1 Frequency (cm-1) Absorbance (a) Ge rod and 15% 13C rod (b) DFT simulation 15% 13C C7 C5 (A) (B) 2142.3 (E) 2154.2 2138.2 2140.0 C12 2105.2 (J) 2116.8 2116.3 (C),(F) (G) (D),(H) (I) C5 single substitutions C5 double substitutions Cn 2100 2110 2120 2130 2140 2150 2160 2170 (D) (H)

Comparison of observed vibrational frequencies (cm-1) of the 4(σu) mode for 12C- substituted isotopomers of linear GeC5Ge with the predictions of B3LYP/cc-pVDZ level calculations. aResults of the DFT-B3LYP/ cc-pVDZ calculation scaled by a factor of 2074.7/2051.0=1.0116. bOverlapped by 3(σu) mode of 13C5. cOverlapped by C5 double-12C isotopomer shift.

(a) Ge rod and 85% 13C rod (b) DFT simulation 85% 13C Frequency (cm-1) Absorbance (a) Ge rod and 85% 13C rod (b) DFT simulation 85% 13C 2070 2080 2090 2100 2110 2120 2130 2140 2150 2077.8 (B´) 2074.7 2080.4 C5 (A´) C5 single substitutions C5 double substitutions 2098.8 (C´),(F´) 2114.4 2120.2 (H´) (I´) (D´) 2116.6 (J´) (E´) (G´)

Conclusion The linear GeC5Ge germanium-carbon chain has been detected for the first time through the dual laser evaporation of graphite and germanium. FTIR isotopic shift measurements and DFT calculations at the B3LYP/cc-pVDZ level confirm the identification of the ν4(σu) vibrational fundamental at 2158.0 cm-1 .

ACKNOWLEDGMENTS The Welch Foundation The Welch Foundation TCU Research and Creative Activities Fund The W.M. Keck Foundation

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