Abstract

Abstract The shapes of vibrational bands in solution can provide detailed information about the dynamics of the system. The band shape and the dynamics are related by the Fourier transform relation between frequency and time. The shape is dependent on whether the band is homogeneously or inhomogeneously broadened. Modern vibrational “echo” experiments can distinguish between the two. Most theories of band broadening assume homogeneous broadening. Various dephasing mechanisms contribute to the homogeneous band shape, and the “echo” experiments can unravel – with some surprising results – these contributions. Under appropriate circumstances, dynamic nuclear magnetic resonance (NMR) can provide detailed information about the rate of chemical exchange processes on a “slow” timescale. Under more restrictive conditions, the change in vibrational band shape with temperature can provide the same information but on a “very fast” timescale.

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