The multistructural method for torsional anharmonicity (MS-T) is employed to compute anharmonic conformationally averaged partition functions which then serve as the basis for the calculation of thermochemical parameters for N2O5 over the temperature range 03000 K, and thermal rate constants for the hydrolysis reaction N2O5 + H2O -> 2 HNO3 over the temperature range 1801800 K. The M06-2X hybrid meta-GGA density functional paired with the MG3S basis set is used to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along the reaction path, with further energy refinement at stationary points obtained via single-point CCSD(T)-F12a/cc-pVTZ-F12 calculations including corrections for corevalence and scalar relativistic effects. The internal rotations in dinitrogen pentoxide are found to generate three structures (conformations) whose contributions are included in the partition function via the MS-T formalism, leading to a computed value for S degrees(298.15)(N2O5) of 353.45 J mol(-1) K-1. This new estimate for S degrees(298.15)(N2O5) is used to reanalyze the equilibrium constants for the reaction NO3 + NO2 = N2O5 measured by Osthoff et al. [ Phys. Chem. Chem. Phys. 2007, 9, 5785-5793] to arrive at Delta H-f degrees(298.15)(N2O5) = 14.31 +/- 0.53 kJ mol(-1) via the third law method, which compares well with our computed ab initio value of 13.53 +/- 0.56 kJ mol(-1). Finally, multistructural canonical variational-transition-state theory with multidimensional tunneling (MS-CVT/MT) is used to study the kinetics for hydrolysis of N2O5 by a single water molecule, whose rate constant can be summarized by the Arrhenius expression 9.51 x 10(-17) (T/298 K)(3.354) e(-(7900K/T)) cm(3) molecule(-1) s(-1) over the temperature range 1801800 K.