title: Finite-temperature hydrogen adsorption and desorption thermodynamics driven by soft vibration modes.
abstract: It has been widely accepted that enhanced dihydrogen adsorption is required for room-temperature hydrogen storage on nanostructured porous materials. Here we report, based on results of first-principles total energy and vibrational spectrum calculations, finite-temperature adsorption and desorption thermodynamics of hydrogen molecules that are adsorbed on the metal center of metal-porphyrin-incorporated graphene. We have revealed that the room-temperature hydrogen storage is achievable not only with the enhanced adsorption enthalpy, but also with soft-mode driven vibrational entropy of the adsorbed dihydrogen molecule. The soft vibration modes mostly result from multiple orbital coupling between the hydrogen molecule and the buckled metal center, for example, in Ca-porphyrin-incorporated graphene. Our study suggests that the current design strategy for room-temperature hydrogen storage materials should be modified with explicitly taking the finite-temperature vibration thermodynamics into account.
authors: Graduate School of Nanoscience and Technology (WCU), KAIST, Daejeon 305-701, Korea.
authors: Sung-Jae
authors: SJ
authors: Woo
authors: Eui-Sup
authors: ES
authors: Lee
authors: Mina
authors: M
authors: Yoon
authors: Yong-Hyun
authors: YH
authors: Kim