Determination of the thermodynamic properties of reactor constituents is the first step in designing control strategies for plasma-mediated deposition processes and is also a key fundamental issue in physical chemistry. In this work, a recently proposed multistructural statistical thermodynamic method is used to show the importance of multiple structures and torsional anharmonicity in determining the thermodynamic properties of silicon hydride clusters, which are important both in plasmas and in thermally driven systems. It includes five different categories of silicon hydride clusters and radicals, including silanes, silyl radicals, and silenes. We employed a statistical mechanical approach, namely the recently developed multistructural (MS) anharmonicity method, in combination with density functional theory to calculate the partition functions, which in turn are used to estimate thermodynamic quantities, namely Gibbs free energy, enthalpy, entropy, and heat capacity, for all of the systems considered. The calculations are performed using all of the conformational structures of each molecule or radical by employing the multistructural quasiharmonic approximation (MS-QH) and also by including torsional potential anharmonicity (MS-T). For those cases where group additivity (GA) results are available, the thermodynamic quantities obtained from our MS-T calculations differ considerably due to the fact that the GA method is based on single-structure data for isomers of each stoichiometry, and hence lack multistructural effects; whereas we find that multistructural effects are very important in silicon hydride systems. Our results also indicate that the entropic effect on the thermochemistry is huge and is dominated by multistructural effects. The entropic effect of multiple structures is also expected to be important for other kinds of chain molecules, and its effect on nucleation kinetics is expected to be large.