Methylstyrenes – Microwave Spectroscopy

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Methylstyrenes – Microwave Spectroscopy cis-β-Methylstyrene trans-β-Methylstyrene Objectives Assign the rotational spectra Compare the potential barriers to methyl internal rotation RANIL M. GURUSINGHE, MICHAEL TUBERGEN Department of Chemistry and Biochemistry, Kent State University, OH.

Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study Fitting Strategy Rotational constants estimated Geometry optimization at ωB97XD/6-311++G(d,p) Barrier height estimated Relaxed potential scan at ωB97XD/6-311++G(d,p) A components were fitted RRFIT, ZFAP Programs A and E components fitted simultaneously XIAM Program Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Equilibrium Structures α-Methylstyrene A (MHz) 3598.5539 B (MHz) 1197.4917 C (MHz) 942.2095 μb=0.33 D > μc=0.15 D > μa=0.02 D cis-β-Methylstyrene A (MHz) 3728.8355 B (MHz) 1093.3866 C (MHz) 902.8941 μa=0.27 D > μb=0.24 D > μc=0.17 D trans-β-Methylstyrene A (MHz) 5045.6034 B (MHz) 867.2295 C (MHz) 745.0565 μa=-0.51 D > μb=0.12 D > μc=-0.04 D Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Relaxed Potential Scans at ωB97XD/6-311++G(d,p) Barrier estimation for trans-β-Methylstyrene α-Methylstyrene cis-β-Methylstyrene trans-β-Methylstyrene Barrier(cm-1) 665.7 704.0 654.9 Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Microwave Rotational Spectra Mini-Cavity FTMW Spectrometer Range : 10.5 – 22.0 GHz Resolution : 2.4 kHz Carrier Gas : 30% He : 70% Ne Backing pressure : 1.5 atm Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Global Fit: cis-β-Methylstyrene Parameter XIAM ωB97XD A (MHz) 3702.3227(3) 3728.8355 B (MHz) 1088.8949(8) 1093.3866 C (MHz) 899.92458(4) 902.8941 ΔJ (kHz) 0.1378(4) - ΔJK (kHz) -0.234(3) ΔK (kHz) 2.178(23) δJ (kHz) -0.00664(16) δK (kHz) 0.949(12) N 144 Δνrms (kHz) 1.866 Parameter XIAM ωB97XD V3 (cm-1) 714(7) 704.0 F0 (GHz) Fixed 152.5 151.9 Iα (uA2) Fixed 3.31 3.33 ε (rad) 0.49(5) 0.47 < (i,a) 80.40(7) 710 < (i,b) 300(2) - < (i,c) 620(2) μa > μb >μc Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Global Fit: trans-β-Methylstyrene Parameter XIAM ωB97XD A (MHz) 5008.8606(16) 5045.6034 B (MHz) 864.68541(10) 867.2295 C (MHz) 741.68899(9) 745.0565 ΔJ (kHz) 0.01812(18) - ΔJK (kHz) 0.1354(10) ΔK (kHz) 0.7(3) δJ (kHz) 0.00257(15) δK (kHz) 0.083(19) N 170 Δνrms (kHz) 1.491 Parameter XIAM ωB97XD V3 (cm-1) 578(3) 654.9 F0 (GHz) 159.9(8) 151.6 Iα (uA2) 3.161(16) 3.33 ε (rad) Fixed 0.00 0.00 < (i,a) 13.20(9) 130 < (i,b) 76.80(9) - < (i,c) 90.00(<0) μa> μb> μc Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

α-Methylstyrene : Preliminary Fits Parameter ωB97XD/ 6-311++G(d,p) ZFAP Fit [A component] XIAM [Global Fit] A (MHz) 3598.5539 3577.0466(8) 3577.0372(9) B (MHz) 1197.4917 1195.9195(5) 1195.92171(22) C (MHz) 942.2095 933.3494(5) 933.3458(3) ΔJ (kHz) - 0.061(6) 0.0658(10) ΔJK (kHz) -0.0411(15) -0.068(14) ΔK (kHz) 0.65(9) 0.45(8) δJ (kHz) 0.0085(6) 0.0061(5) δK (kHz) 0.57(4) 0.72(3) V3 (cm-1) 665.7 603 (8) ε (rad) 0.44 Fixed 0.44 < (i,a) 59.50 50.30(9) N 39 69 Δνrms (kHz) 4.835 6.381 Only the transitions with Ka= 0,1 were fitted μb> μc > μa Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study Transitions with Ka = 2, 3 330-221 4 lines ?? 432-423 4 lines ?? 634-625 3 lines ?? Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Propenyl/Benzene Internal Rotation Relaxed potential scan at ωB97XD/6-311++G(d,p) Barrier Heights = 471.3 cm-1, 230.1 cm-1 Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Conclusion Assigned the microwave rotational spectra and determined the potential barrier to internal rotation of cis-β-Methylstyrene, trans-β-Methylstyrene. Preliminary XIAM fit of α-Methylstyrene can not fit Ka = 2,3 transitions Additional fitting in α-Methylstyrene is probably due to the large amplitude motion of the propenyl (CH2-CH-CH3 )/ Benzene. A (MHZ) B (MHz) C (MHz) Exp. V3(cm-1) Calc. V3(cm-1) cis-β-Methylstyrene 3702.3227(3) 1088.8949(8) 899.92458(4) 714(7) 701.25 trans-β-Methylstyrene 5008.8606(16) 864.68541(10) 741.68899(9) 578(3) 654.90 Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study

Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study Acknowledgement Ohio Supercomputer center Kent State University Methylstyrenes – Internal Rotation: Microwave Spectroscopic Study