Enhancing the efficiency of the Rankine cycle, which is utilized for multiple renewable energy sources, requires the use of a working fluid with a high latent heat of vaporization. To further enhance its latent heat, a working fluid can be placed in a metal organic heat carrier (MOHC) with a high heat of adsorption. One such material is Ni\DOBDC, in which linear alkanes have a higher heat of adsorption than cyclic alkanes. We carried out molecular dynamics simulations to investigate the structural, diffusive, and adsorption properties of n-hexane and cyclohexane in Ni\DOBDC. The strong binding for both n-hexane and cyclohexane with Ni\DOBDC is attributed to the increase of the heat of adsorption observed in experiments. Our structural results indicate the organic linkers in Ni\DOBDC are the primary binding sites for both n-hexane and cyclohexane molecules. However, at all temperatures and loadings examined in present work, n-hexane clearly showed stronger binding with Ni\DOBDC than cyclohexane. This was found to be the result of the ability of n-hexane to reconfigure its structure to a greater degree than cyclohexane to gain more contacts between adsorbates and adsorbents. The geometry and flexibility of guest molecules were also related to their diffusivity in Ni\DOBDC, with higher diffusion for flexible molecules. Because of the large pore sizes in Ni\DOBDC, energetic effects were the dominant force for alkane adsorption and selectivity.