Terahertz (THz) spectroscopic investigations of condensed-phase biological samples are reviewed ranging from the simple crystalline forms of amino acids, carbohydrates and polypeptides to the more complex aqueous forms of small proteins, DNA and RNA. Vibrationally resolved studies of crystalline samples have revealed the exquisite sensitivity of THz modes to crystalline order, temperature, conformational form, peptide sequence and local solvate environment and have given unprecedented measures of the binding force constants and anharmonic character of the force fields, properties necessary to improve predictability but not readily obtainable using any other method. These studies have provided benchmark vibrational data on extended periodic structures for direct comparisons with classical (CHARMm) and quantum chemical (density functional theory) theories. For the larger amorphous and/or aqueous phase samples, the THz modes form a continuum-like absorption that arises because of the full accessibility to conformational space and/or the rapid time scale for inter-conversion in these environments. Despite severe absorption by liquid water, detailed investigations have uncovered the photo- and hydration-induced conformational flexibility of proteins, the solvent shell depth of the water/biomolecule boundary layers and the solvent reorientation dynamics occurring in these interfacial layers that occur on sub-picosecond time scales. As such, THz spectroscopy has enhanced and extended the accessibility to intermolecular forces, length- and timescales important in biological structure and activity.

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The pure rotational spectrum of ethyl sulfide has been measured from 12 to 21 GHz in a 1 K jet-cooled expansion using a Fourier-transform microwave (FTMW) spectrometer. Prominent features in the spectrum are assigned to transitions from three conformational isomers. Additional assignments of the 13C and 34S isotopomer spectra of these conformers effectively account for all of the remaining transitions in the spectrum. Accurate “heavy-atom” substitution structures are obtained via a Kraitchman analysis of 14 rotational parameter sets, permitting definitive identification of the molecular structures of the three conformers. Two of the structures designated as the gauche–gauche (GG) and trans–trans (TT) conformers have symmetric forms with C2 and C2v symmetries, respectively, and the third trans–gauche (TG) configuration is asymmetric. The components of the electric dipole moment along the principal inertial axes have been determined from Stark measurements and are consistent with these structural assignments. Detailed comparisons are made with the calculated geometries, dipole moments, and energy-level ordering at both the HF (Hartree–Fock)/6-31* and MP2 (second-order Møller–Plesset)/6-311** levels of theory. Significant discrepancies are found, which are mainly attributed to errors in the calculated dihedral angles that define the different conformations. A graphical-user-interface computer program has aided in the identification and assignment of entangled hybrid-band spectra from the different conformers and isotopomers in this study. The program includes features that enable real-time refinement of rotational constants and hybrid band intensities through visual comparisons of the experimental data with simulated spectra. Capacities also exist to rapidly assign quantum number labels for least-squares fitting purposes.