Chirped-pulsed FTMW Spectrum of 4-Fluorobenzyl Alcohol

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Chirped-pulsed FTMW Spectrum of 4-Fluorobenzyl Alcohol Chirped-pulsed FTMW Spectrum of 4-Fluorobenzyl Alcohol. Structure and Torsional Motions in the Ground Electronic State Phase. Ryan G. Bird, and David W. Pratt University of Pittsburgh Justin L. Neill and Brooks H. Pate University of Virginia

Excited State Spectroscopy FBA electronic spectrum 4 band caused by 2 internal rotations Difficult to separate S0 and S1 barriers Use CP-FTMW to study S0 0.2cm-1

Methyl Internal Rotation Internal rotation cause perturbations Ĥ = ĤRot + ĤInt Three types of rotor High barrier, Low barrier, Asymmetric Difficulties in assigning spectra1 JB95, SPCAT, XIAM 1Kleiner, I. Journal of Molecular Spectroscopy 2010, 260, 1

CP-FTMW Spectrometer MW Synthesizer Arbitrary Waveform Generator Fourier Transform Free Induction Decay Chirped Pulse 240 MHz 500 MHz Digitizer (10 Gs/s)

o-Toluidine 10000 avg 500 MHz CP

High Barrier: o-Toluidine + - Ĥ = ĤRot + ĤInt + ĤQuad ĤRot ›› Ĥint ĤQuad › Ĥint Barrier high; Tunneling splitting low JB95, XIAM, SPFIT Torsion angle 60 180 300 700 cm-1 E A Morgan, P. J.; Alvarez-Valtierra, L.; Pratt, D. W. The Journal of Physical Chemistry A 2009, 113, 13221-13226.

o-Toluidine Constants A Band E Band A (MHz) 3230.29(1) 3230.35(2) B (MHz) 2188.807(1) 2188.827(2) C (MHz) 1316.940(3) 1316.943(5) χaa (MHz) 2.007(7) 2.02(1) χbb (MHz) 2.05(1) 2.04(2) χcc (MHz) -4.06(1) -4.07(2) DJ (kHz) 0.35(8) 0.5(1) DJK (kHz) -1.4(3) -2.0(5) DK (kHz) -4(4) -4(7) dJ (kHz) 0.17(5) 0.26 (7) dK(kHz) -0.4(6) 0.5(9) ΔI (amu Å2) -3.590 -3.586 Lines 52 53 F = 4←3 312-211 10000 avg 10 MHz CP A E F = 3←2 A E F = 2←1 A E F = 2←2 A E

m-Toluidine 10000 avg 500 MHz CP

Low Barrier: m-Toluidine Ĥ = ĤRot + ĤInt + ĤQuad ĤRot ≈ Ĥint Barrier low; Tunneling splitting high JB95, XIAM Torsion angle 60 180 300 A E 9 cm-1 Morgan, P. J.; Alvarez-Valtierra, L.; Pratt, D. W. The Journal of Physical Chemistry A 2009, 113, 13221-13226.

m-Toluidine Constants XIAM A (MHz) 3635.9(1) B (MHz) 1791.20(8) C (MHz) 1210.31(5) χaa (MHz) 2.3(6) χbb (MHz) 1.9(6) χcc (MHz) -4.2(6) DJ (kHz) 2(1) DJK (kHz) -2(2) DK (kHz) -31(12) dJ (kHz) 0.8(5) dK(kHz) 23(7) V3 (cm-1) 4.23(6) ΔI (amu Å2) -0.52 Lines 79

4-Fluorobenzyl Alcohol

FBA: Asymmetric Rotor 0- 0+ CH2OH rotor results in a 2-fold barrier Rotor axis is mainly along a-axis µa and µb-type transitions ΔE between 0+ and 0- is small µb-type transitions are Coriolis interactions between levels 0+ 0- 0+ 0- a b

FBA Constants FBA LIF1 Benzyl Alcohol2 A 0+ (MHz) 4628.9(20) 4758.986(1) B 0+ (MHz) 928.5(10) 1475.398(1) C 0+ (MHz) 803.1(6) 1193.4018(5) A 0- (MHz) 4628.3(15) 4759.133(1) B 0- (MHz) 928.9(10) 1475.409(1) C 0- (MHz) 803.8(10) 1193.3769(5) Fab (MHz) 222.021(8) Fbc (kHz) 57.418(1) ΔE (MHz) 492.816(2) 1Nikolaev, A. E, In Preparation 2Utzat, K. A.; Bohn, R. K.; Montgomery, J. A.; Michels, H. H.; Caminati, W. The Journal of Physical Chemistry A.

Barrier Problems Challenging to measure High Barriers > 500 cm-1 o-toluidine ≈ 700 cm-1 JB 95, SPCAT, XIAM Challenging to simulate Low Barriers m-toluidine = 4.2 cm-1 Free rotor limit Challenging to fit Asymmetric Rotor FBA: µb and µc >> µa Coriolis terms have large effect on µb/µc frequencies

Acknowledgements Pratt Group: Pate Group: Dr. David Pratt Dr. Brooks Pate Justin Young Justin Neill A.J. Fleisher Matt Muckle Phil Morgan Daniel Zaleski Jessica Thomas Amanda Steber Casey Clements Patrick Walsh Dr. Vanessa Vaquero

o-Toluidine Constants Experimental LIF1 MP2/6-31G+g(d) A Band E Band A (MHz) 3230.29(1) 3230.35(2) 3230.9(1) 3228.5(1) 3227.85 B (MHz) 2188.807(1) 2188.827(2) 2189.0(1) 2189.1(1) 2178.171 C (MHz) 1316.940(3) 1316.943(5) 1316.8(1) 1316.9(1) 1313.306 χaa (MHz) 2.007(7) 2.02(1) χbb (MHz) 2.05(1) 2.04(2) χcc (MHz) -4.06(1) -4.07(2) DJ (kHz) 0.35(8) 0.5(1) DJK (kHz) -1.4(3) -2.0(5) DK (kHz) -4(4) -4(7) dJ (kHz) 0.17(5) 0.26 (7) dK(kHz) -0.4(6) 0.5(9) ΔI (amu Å2) -3.590 -3.586 -3.51 -3.65 -3.768 Lines 52 53 1Morgan, P. J.; Alvarez-Valtierra, L.; Pratt, D. W. The Journal of Physical Chemistry A 2009, 113, 13221-13226.

m-Toluidine Constants Experimental LIF1 MP2/6-31G** A Band E Band A (MHz) 3700.847(4) 3701.3(1) 3700.2(1) 3637.741 B (MHz) 1795.884(4) 1795.9(1) 1795.4(1) 1796.290 C (MHz) 1210.344(4) 1210.4(1) 1210.3(1) 1211.494 χaa (MHz) 2.18 (5) χbb (MHz) 2.05(5) χcc (MHz) -4.23(5) DJ (kHz) 0.12(5) DJK (kHz) -0.6(1) DK (kHz) 1.2(5) dJ (kHz) 0.03(2) dK(kHz) 0.06(40) ΔI (amu Å2) -0.40 -0.414 -0.508 Lines 60 1Morgan, P. J.; Alvarez-Valtierra, L.; Pratt, D. W. The Journal of Physical Chemistry A 2009, 113, 13221-13226.