Biomedical subjects

Ryohei Kishi

Publications and source records attributed to Ryohei Kishi.

6 recordsLinked to original sources

PubMed2006

Exciton recurrence motion in aggregate systems in the presence of quantized optical fields.

The exciton dynamics of model aggregate systems, dimer, trimer, and pentamer, composed of two-state monomers is computationally investigated in the presence of three types of quantized optical fields, i.e., coherent, amplitude-squeezed, and phase-squeezed fields, in comparison with the case of classical laser fields. The constituent monomers are assumed to interact with each other by the dipole-dipole interaction, and the two-exciton model, which takes into account both the one- and two-exciton generations, is employed. As shown in previous studies, near-degenerate exciton states in the presence of a (near) resonant classical laser field create quantum superposition states and thus cause the spatial exciton recurrence motion after cutting the applied field. In contrast, continuously applied quantized optical fields turn out to induce similar exciton recurrence motions in the quiescent region between the collapse and revival behaviors of Rabi oscillation. The spatial features of exciton recurrence motions are shown to depend on the architecture of aggregates. It is also found that the coherent and amplitude-squeezed fields tend to induce longer-term exciton recurrence behavior than the phase-squeezed field. These features have a possibility for opening up a novel creation and control scheme of exciton recurrence motions in aggregate systems under the quantized optical fields.

Journal Article↗

PubMed2006

Origin of the enhancement of the second hyperpolarizability of singlet diradical systems with intermediate diradical character.

The origin of the diradical character dependence of the second hyperpolarizability (gamma) of neutral singlet diradical systems is clarified based on the perturbation formula of gamma using the simplest diradical molecular model with different diradical characters, i.e., H2 under bond dissociation. The enhancement of gamma in the intermediate diradical character region turns out to originate from the increasing magnitude of the transition moment between the first and second excited states and the decrease of that between the ground and first excited states, respectively, with the increase in diradical character. This feature confirms that open-shell singlet conjugated molecules with intermediate diradical characters constitute a new class of third-order nonlinear optical systems, whose gamma values can be controlled by the diradical character in addition to the conjugation length.

Journal Article↗

PubMed2006

Second hyperpolarizabilities (gamma) of bisimidazole and bistriazole benzenes: diradical character, charged state, and spin state dependences.

The second hyperpolarizabilities of bisimidazole- and bistriazole-benzene compounds have been calculated at different levels of approximation to unravel the effects of diradical character as well as of charge and spin multiplicity. The largest second hyperpolarizabilities are associated with intermediate diradical character, provided positive charging does not compensate for this effect. For the neutral diradical bisimidazole compound, the singlet diradical species possesses a second hyperpolarizability two to three times larger than the corresponding triplet, demonstrating the possibility of spin state control of the third-order NLO responses for diradical species.

Benzene Derivatives↗

PubMed2005

Quantum master equation approach to the second hyperpolarizability of nanostar dendritic systems.

We investigate the dynamic second hyperpolarizability (gamma) of nanostar dendritic systems using the quantum master equation approach. In the nanostar dendritic systems composed of three-state monomers, the multistep exciton states are obtained by the dipole-dipole interactions, and the directional energy transport, i.e., exciton migration, from the periphery to the core is predicted to occur by the relaxation between exciton states originating in the exciton-phonon coupling. The effects of the intermolcecular interaction and the exciton migration, i.e., exciton relaxation, on the gamma in the third-harmonic generation (THG) are examined in the three-photon off- and on- resonance regions using the two-exciton model. Furthermore, the method for analysis of spatial contributions of excitons to gamma is presented by partitioning the total gamma into the one- and two-exciton contributions. It turns out that the exciton relaxation between exciton states causes significant broadening of the spectra of gamma and their mutual overlap as well as the relative increase of two-exciton contributions in the nanostar dendritic system.

Models, Chemical↗

PubMed2005

Second hyperpolarizability (gamma) of singlet diradical system: dependence of gamma on the diradical character.

The dependence of the second hyperpolarizability (gamma) on the diradical character (y) for singlet diradical systems is investigated using a model compound, the p-quinodimethane (PQM) molecule with different both-end carbon-carbon (C-C) bond lengths, by several ab initio molecular orbital and density functional theory methods. The diradical character based on UHF calculations indicates that at equilibrium geometry PQM is in a singlet ground state and primarily exhibits a quinoid structure, whereas the diradical character increases when increasing both-end C-C bond lengths. At the highest level of approximation, that is, using the UCCSD(T) method with the 6-31G+diffuse p (zeta = 0.0523) basis set, the longitudinal static gamma of PQM presents a maximum value for intermediate diradical character (y approximately 0.5) while the gamma values are larger for intermediate and large diradical character (y approximately 0.5-0.7) than for small diradical character (y < 0.2). This feature suggests that the gamma values of singlet diradical systems in the intermediate and somewhat strong correlation regimes are significantly enhanced as compared to those in the weak correlation regime. These results are substantiated by a complementary study of the variation in gamma upon twisted ethylene.

Journal Article↗

PubMed2004

Exciton migration dynamics in a dendritic molecule: quantum master equation approach using ab initio molecular orbital configuration interaction method.

We investigate the exciton migration dynamics in a dendritic molecular model composed of pi-conjugation linear-leg units (acetylenes and diacetylene) and a benzene ring (branching point) using the quantum master equation approach with the ab initio molecular orbital (MO) configuration interaction (CI) method. The efficient migration of exciton from short-length linear legs (acetylenes) to long-length linear leg (diacetylene) via a benzene ring is observed. As predicted in previous studies, the exciton (electron and hole) distributions are relatively well localized in each generation segmented by the meta-branching point (meta-substituted benzene ring) though the electron and hole distributions are delocalized and are somewhat spatially different from each other within each generation. It is found that the excitons localized in the generation composed of short linear legs occupy in higher-lying exciton states, while those in the generation composed of long linear legs do in lower-lying ones. These features suggest the decoupling of pi-conjugation at the meta-branching point. On the other hand, the relaxation effect between exciton states is found to be caused by the exciton-phonon coupling, in which the existence of common configurations (electron-hole pairs) in CI wave functions between adjacent exciton states (having primary distributions on short and long linear-leg regions, respectively) is important for the relaxation between their exciton states. This feature indicates the importance of partial penetration of pi-conjugation through the meta-substituted benzene ring in excited states for such exciton migration.

Journal Article↗