10.1021/jz401181q.s001 Eugene Kamarchik Eugene Kamarchik Ahren W. Jasper Ahren W. Jasper Anharmonic Vibrational Properties from Intrinsic <i>n</i>‑Mode State Densities American Chemical Society 2015 density CH C 3H Truncation state densities Anharmonic Vibrational Properties method anharmonic vibrational result energy surface mode pairing partition functions anharmonic vibrational state counts modes yields quantity 2015-12-16 23:15:09 Journal contribution https://acs.figshare.com/articles/journal_contribution/Anharmonic_Vibrational_Properties_from_Intrinsic_i_n_i_Mode_State_Densities/2024784 A method for calculating fully anharmonic vibrational state counts, state densities, and partition functions for molecules is presented. The method makes use of a new quantity, the <i>intrinsic</i> density of states, which is associated with the states that uniquely arise from a given mode, mode pairing, or higher-order mode coupling. By using only low-order intrinsic densities, the fully coupled anharmonic vibrational result can be constructed, as shown by our application of the method to methane, CH<sub>4</sub>, and cyclopropene, C<sub>3</sub>H<sub>4</sub>. Truncation of the intrinsic expansion at the coupling of pairs of modes yields greatly improved scaling over direct evaluation of the full-dimensional result and recovers a large fraction of the total anharmonicity. We also discuss the relation of the new quantities to the structure of the potential energy surface.