Supporting Information Infrared Detection of the 1,3-Dimethyl Cyclopentadienyl Cation, an Isomer of Protonated Toluene Jonathan D. Mosley, Justin W. Young, Michael A. Duncan* Department of Chemistry, University of Georgia, Athens, GA 30602, U.S.A. *Corresponding author: [email protected]*Phone: +1-706-542-1998
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Supporting Information
Infrared Detection of the 1,3-Dimethyl Cyclopentadienyl Cation, an Isomer of Protonated Toluene
Jonathan D. Mosley, Justin W. Young, Michael A. Duncan*
Department of Chemistry, University of Georgia, Athens, GA 30602, U.S.A.*Corresponding author: [email protected]
Figure S1. The optimized geometry of 1 (Cs symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 1 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S2. The optimized geometry of 2 calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 2 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S3. The optimized geometry of 3 calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 3 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S4. The optimized geometry of 4' (Cs symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 4' calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S5. The optimized geometry of 4 (Cs symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 4 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S6. The optimized geometry of 5 calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 5 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S7. The optimized geometry of 6 (C2 symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 6 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S8. The optimized geometry of 7 (Cs symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 7 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S9. The optimized geometry of 8 calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 8 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S10. The optimized geometry of 9 (C2v symmetry) calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 9 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S11. The optimized geometry of 10 calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 10 calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C and H atoms.
Figure S12. Experiment compared to theory for 1,3-dimethyl cyclopentenyl cation. Predicted vibrations were computed at the B3LYP/6-311+G(d,p) level of theory using GAMESS-US. A 0.981 scale factor was used in the fingerprint region and a 0.966 scale factor was used in the C−H stretching region.
Figure S13. The optimized geometry of 1 (Cs symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 1 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S14. The optimized geometry of 2 calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 2 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S15. The optimized geometry of 3 calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 3 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S16. The optimized geometry of 4' (Cs symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 4' calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S17. The optimized geometry of 4 (Cs symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 4 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S18. The optimized geometry of 5 calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 5 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S19. The optimized geometry of 6 (C2 symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 6 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S20. The optimized geometry of 7 calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 7 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S21. The optimized geometry of 8 calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 8 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S22. The optimized geometry of 9 (C2v symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 9 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Figure S23. The optimized geometry of 10 (C2v symmetry) calculated at the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms. Bond lengths (black) are in Angstroms. Bond angles (red) are in degrees.
The normal mode frequencies (unscaled) and intensities (km/mol) of 10 calculatedat the MP2(fc) level of theory using GAMESS-US. The aug-cc-pVDZ basis set was used for C and H atoms.
Table S2. Selected isomers of C7H11+Ar calculated at the B3LYP level of theory using
GAMESS-US. Relative energies (∆E) are zero-point vibrational energy corrected. Binding energies (B.E.) are not corrected for zero point vibrational energy or basis set superposition errors.
Figure S24. The optimized geometry of 1−Ar calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C, H and Ar atoms. Bond lengths (black) are in Angstroms.
The normal mode frequencies (unscaled) and intensities (km/mol) of 1−Ar calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C, H and Ar atoms.
Figure S25. The optimized geometry of 9−Ar calculated at the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C, H and Ar atoms. Bond lengths (black) are in Angstroms.
The normal mode frequencies (unscaled) and intensities (km/mol) of 9−Ar calculatedat the B3LYP level of theory using GAMESS-US. The 6-311+G(d,p) basis set was used for C, H and Ar atoms.