The observed infrared band shape of CO2 antisymmetric stretch mode in acetonitrile: (a) the observed band (thick gray line) and its single Lorentzian fit (thin black line) and (b) the observed band (thick gray line, hot band subtracted) and its curve fit (thin solid line) by the sum of two Lorentzians (dashed and dotted lines).
Computed correlation functions and the corresponding band shape by the MD simulation: (a) the vibrational correlation function (solid) and its single exponential fit (dotted), (b) the rotational correlation function (solid) and its single exponential fit (dotted), (c) a Hamming apodization function and (d) the computed band shape (solid) and the observed (dotted) infrared band shape.
Rotational correlation functions obtained by the m-diffusion model: (a) τ = ∞, 0.7, 0.2, 0.08, 0.04 ps from the bottom to top and (b) rotational correlation function of CO2 in acetonitrile by the MD simulation (gray solid line) and correlation functions by the m-diffusion model (black dotted line) with τ = 0.2, 0.16, 0.12, 0.08, 0.04 ps from the bottom to top.
The observed Raman band shape of CO2 symmetric stretch mode in acetonitrile: (a) the observed parallel (I XX , solid) and perpendicular (I XZ , dotted) scattering intensities and (b) the calculated isotropic (I iso, gray circle) and anisotropic (I aniso, black circle) components, and their Voigt function fits (gray and black solid lines, respectively).
Raman rotational broadening calculated by the Lorentzian approximation (dotted line) and by the direct deconvolution of I aniso by I iso (thick gray line), compared to the MD simulation (black line).
The observed time-resolved infrared absorption anisotropy: (a) parallel (filled circle) and perpendicular (open circle) absorptions of 13CO2 in ethanol and (b) the calculated anisotropy (circle) and its single exponential fit (line).
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