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This thesis is concerned with study of vibrational dynamics and their effect on charge transport in thin films of organic semiconductors. Two classes of organic semiconductors are investigated- crystalline small molecules and conjugated polymers. Although device performance of both classes of materials has greatly improved over last two decades, detailed understanding of relationship between structure and transport properties is still missing- so far development of organic semiconductors has mostly been based on experimental approach, with theoretical models providing post factum justification rather than guiding rational design of novel compounds. In this thesis I establish methodology to investigate both inter- and intramolecular vibrational modes by combining latest computational techniques with experimental pressure-dependent Raman spectroscopy. The dominant factor limiting charge delocalization in crystalline small molecules are low frequency, large amplitude intermolecular modes. However, theoretical modeling of these modes require use of periodic boundary conditions increasing computational cost by orders of magnitude when compared to commonly used vacuum phase simulations. I report comparative study of two implementations (CRYSTAL09 and CASTEP) of density functional theory (DFT) and dispersion correction (Grimme and Tkatchenko-Scheffler) and evaluate their applicability to predict low frequency vibrational modes in 2,7-Dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) and 2,8-Difl uoro-5,11-bis(triethylsilylethynyl)anthradithiophene (dif-TES-ADT). Charge transport in conjugated polymers is strongly affected by energetic disorder arising from spatial variations in backbone conformation. I combine vacuum phase DFT simulations of intramolecular vibrational modes with pressure-dependent Raman spectroscopy to study planarity and torsional backbone disorder of 2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene (pBTTT), indacenodithiophene-co-benzo-thiadiazole (IDT-BT), diketopyrrolopyrrole-benzotriazole (DPP-BTZ) and naphtalene-bithiophene (NDI-T2) at pressures up to 3.9 GPa. It is shown that Raman spectra of pBTTT and NDI-T2 demonstrate dependence of mode intensities on hydrostatic pressure, whereas spectra of IDT-BT and DPP-BTZ exhibit lack of dependence. Simulations of theoretical spectra performed as a function of backbone torsion indicate that pBTTT undergoes deplanarization of already non-planar backbone and that NDI-T2 backbone is planarized, whereas backbones of IDT-BT and DPP-BTZ are resilient to changes of conformation. Finally, I perform large scale molecular dynamics simulations of crystalline, semi-crystalline and disordered phases of IDT-BT and DPP-BT in order to investigate effect of disorder on backbone conformation. Both compounds were previously reported to exhibit extremely low degree of energetic disorder- I assign this phenomenon to their surprisingly strong resilience to side chain disorder. In both systems simulations demonstrate novel mechanism of disorder accommodation- their backbones bend rather than twist and retain low degree of torsional variation even in amorphous phase., The Engineering and Physical Sciences Research Council