title: Theoretical Investigations on the Photoinduced Phase Transition Mechanism of Tetrathiafulvalene-p-chloranil.
abstract: The photoinduced phase transition (PIPT) mechanism of tetrathiafulvalene-p-chloranil (TTF-CA) molecular crystal was theoretically investigated using the long-range corrected time-dependent density functional theory (LC-TDDFT) combined with a local response dispersion (LRD) method, which enables us to quantitatively reproduce charge transfer (CT) excitations of van der Waals clusters. By calculating the excitation spectrum and potential energy surface, we found that the PIPT of TTF-CA crystal may proceed through the angle change of the molecular planes. We also found that the CT excitation of one TTF-CA pair helps other neighboring TTF-CA pairs to become excited. Consequently, we theoretically proposed the initial structural change in the neutral-to-ionic PIPT of TTF-CA crystal, which is consistent with experiments.
authors.affiliation: Advanced Science Institute , RIKEN 2-1, Hirosawa, Wako, Saitama 351-0198, Japan.|CREST, Japan Science and Technology Agency , Saitama 332-0012, Japan.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Nakatsuka
authors.affiliation: Advanced Science Institute , RIKEN 2-1, Hirosawa, Wako, Saitama 351-0198, Japan.|CREST, Japan Science and Technology Agency , Saitama 332-0012, Japan.
authors.forename: Takao
authors.initials: T
authors.lastname: Tsuneda
authors.affiliation: Photon Science Center of the University of Tokyo , Tokyo 113-8656, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Sato
authors.affiliation: Advanced Science Institute , RIKEN 2-1, Hirosawa, Wako, Saitama 351-0198, Japan.|CREST, Japan Science and Technology Agency , Saitama 332-0012, Japan.
authors.forename: Kimihiko
authors.initials: K
authors.lastname: Hirao