Brooks H. Pate, Gordon G. Brown, and Justin L. Neill

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Presentation transcript:

Lineshape Analysis of Dynamic Rotational Spectra in the Presence of Internal Angular Momentum Brooks H. Pate, Gordon G. Brown, and Justin L. Neill Department of Chemistry University of Virginia

Dynamic Rotational Spectroscopy Rotational Spectroscopy of Highly Vibrationally Excited Molecules Intramolecular Vibrational Energy Redistribution (IVR) Causes Time-Dependent Molecular Structure These dynamics lead to frequency modulation effects known in NMR spectroscopy (Dynamic NMR: motional narrowing and coalescence)

New Effects Unique to Rotational Motion: Gyroscope Dynamics from Internal Angular Momentum Methylbutenyne V3 = 700 cm-1

Rotational Transitions MBEY Transition Intensities MBEY A Sym. E Sym. Kr = 0 (Gyro.) Kr = 0 (Gyro.) Ka = 0 (Asym.) Ka = 0 (Asym.) A Sym. E Sym.

Molecular Parameters for methyl butenyne and butynone Inertia Ellipsoid for MBEY * qTOP = 59.2° Principal Axis (Asymmetric Limit) * qRAM = 35.7° * V3 = 706 cm-1 m r Axis (Gyroscope Limit) * S.L. Hsu, W.H. Flygare; J. Mol. Spec. 32 (1969) 375. Inertia Ellipsoid for Butynone m * qTOP = 62.3° Principal Axis (Asymmetric Limit) * qTOP = 36.8° * V3 = 375 cm-1 r Axis (Gyroscope Limit) * O.L. Stiefvater, J. Sheridan; Proc. Chem. Soc. 1963 (Dec.) 368.

Coalescence Phenomenon B kr kf Lifetime Broadening Frequency Pulling Coalescence Narrowing No Reaction Increasing Reaction Rate

Gyroscope Dynamics C: Coalescence Parameter

Gyroscope Dynamics C: Coalescence Parameter N: Narrowing Parameter (Friction)

Gyroscope Coalescence E Pentenyne 2D IR – CPFTMW Double Resonance Scan Gyroscope Coalescence J = 3 -2 J = 2 - 1

Methylbutenyne Dynamic Rotational Spectrum IR Prepares J=0 Exclusively through P(1) Excitation J = 1 - 0

Vinyl Isocyanate Torsional Potential Dynamic Rotational Spectroscopy State mixing Rigid rotor Justin L. Neill: WG08

3164 cm-1 band Monitor 202101 R(1) Laser pumps all three J = 21 a-type transitions at once; population in 101 of GS is much greater than that in 111 or 110, so most of excited population is in 202

Conclusions and Acknowledgements Intramolecular dynamics can be studied through line shape analysis of the rotational spectra of highly excited molecules Dynamic spectroscopy effects not limited to geometry changes Funding: NSF Experimental Physical Chemistry and NSF MRI Program

Dynamic Rotational spectrum of molecules with sources of internal angular momentum Methyl Butenyne rTOT = 99.8 states/cm-1 rABOVE = 13.5 12 Butynone rTOT = 31.4 states/cm-1 rABOVE = 12.7