Mechanism of quantum chaos in molecular nonadiabatic electron dynamics.

The quantum nuclear kinematic interactions with electrons (or nonadiabatic interactions) are the inherent driving force that possibly causes a mixture of the adiabatic electronic states in molecules. Particularly in systems whose electron wavepackets lie in a densely quasi-degenerate electronic-state manifold where many-dimensional and many-state nonadiabatic interactions last continually, we have found before that those extensive mixings can lead to a quantum electronic-state chaos [K. Takatsuka and Y.

Sonification of molecular electronic energy density and its dynamics.

A method is proposed for sonification of the molecular electronic energy density. The characteristic energetic structures of the individual complicated electronic wavefunctions are extracted in terms of the Energy Natural Orbitals (ENO), which are the eigenfunctions of the electronic energy density operator [K. Takatsuka and Y.

Geometrical decomposition of nonadiabatic interactions to collective coordinates in many-dimensional and many-state mixed fast-slow dynamics.

In general, for many-dimensional and many-state nonadiabatic dynamics composed of slow and fast modes, we geometrically decompose the nonadiabatic interactions by means of the method of singular value decomposition. Each pair of the left and right singular vectors connecting the slow (nuclear) and fast (electronic) modes gives rise to a one-dimensional collective coordinate, and the sum of them amounts to the total nonadiabatic interaction. The analysis identifies how efficiently the slow modes, thus decomposed, can induce a transition in their fast counterparts.

Spin current in the early stage of radical reactions and its mechanisms.

We study the electronic spin flux (atomic-scale flow of the spin density in molecules) by a perturbation analysis and ab initio nonadiabatic calculations. We derive a general perturbative expression of the charge and spin fluxes and identify the driving perturbation of the fluxes to be the time derivative of the electron-nucleus interaction term in the Hamiltonian. We then expand the expression in molecular orbitals so as to identify relevant components of the fluxes.

Electronic-state chaos, intramolecular electronic energy redistribution, and chemical bonding in persisting multidimensional nonadiabatic systems.

We study the chaotic, huge fluctuation of electronic state, resultant intramolecular energy redistribution, and strong chemical bonding surviving the fluctuation with exceedingly long lifetimes of highly excited boron clusters. Those excited states constitute densely quasi-degenerate state manifolds. The huge fluctuation is induced by persisting multidimensional nonadiabatic transitions among the states in the manifold.

Establishment of an unfed strain of and analysis of associated bacterial communities controlling its proliferation.

The ciliate harbors several hundred symbiotic algae in its cell and is widely used as an experimental model for studying symbiosis between eukaryotic cells. Currently, various types of bacteria and eukaryotic microorganisms are used as food for culturing ; thus, the cultivation conditions are not uniform among researchers. To unify cultivation conditions, we established cloned, unfed strains that can be cultured using only sterile medium without exogenous food.

Energy natural orbital characterization of nonadiabatic electron wavepackets in the densely quasi-degenerate electronic state manifold.

Dynamics and energetic structure of largely fluctuating nonadiabatic electron wavepackets are studied in terms of Energy Natural Orbitals (ENOs) [K. Takatsuka and Y. Arasaki, J.

Quantum Chaos in the Dynamics of Molecules.

Quantum chaos is reviewed from the viewpoint of "what is molecule?", particularly placing emphasis on their dynamics. Molecules are composed of heavy nuclei and light electrons, and thereby the very basic molecular theory due to Born and Oppenheimer gives a view that quantum electronic states provide potential functions working on nuclei, which in turn are often treated classically or semiclassically. Therefore, the classic study of chaos in molecular science began with those nuclear dynamics particularly about the vibrational energy randomization within a molecule.

Real-time electronic energy current and quantum energy flux in molecules.

Intra- and inter-molecular electronic energy current is formulated by defining the probability current of electronic energy, called the energy flux. Among vast possible applications to electronic energy transfer phenomena, including chemical reaction dynamics, here we present a first numerical example from highly excited nonadiabatic electron wavepacket dynamics of a boron cluster B.

Nodular hepatic lesion mimicking gallbladder carcinoma in myeloma.

An 81-year-old man was diagnosed with nodular hepatic lesion of extramedullary plasmacytoma with the absence of FDG uptake. Doppler ultrasonography showed pulsations and abundant blood flow signals within the tumor. The blood flow was temporally reduced after daratumumab-based induction therapy; however, the tumor rapidly re-expanded with blood reflow.

Lateral Interbody Fusion for Hyperlordosis and Negative Sagittal Vertical Axis Because of Accordion Phenomenon: A Case Report.

Case: The accordion phenomenon is defined as the difference in the disc space observed on x-ray or computed tomography images taken in both standing and supine positions, which results in a discrepancy of local spinal alignment. Oblique lateral interbody fusion (OLIF) is a less invasive method of potentially correcting both coronal and sagittal spinal alignment. We present the case of a 66-year-old woman with rheumatoid arthritis treated with OLIF for degenerative disc disease presenting with hyperlordosis and negative sagittal vertical axis (SVA) because of the accordion phenomenon.

Nature of chemical bond and potential barrier in an invariant energy-orbital picture.

Physical nature of the chemical bond and potential barrier is studied in terms of energy natural orbitals (ENOs), which are extracted from highly correlated electronic wavefunctions. ENO provides an objective one-electron picture about energy distribution in a molecule, just as the natural orbitals (NOs) represent one electron view about electronic charge distribution. ENO is invariant in the same sense as NO is, that is, ENOs converge to the exact ones as a series of approximate wavefunctions approach the exact one, no matter how the methods of approximation are adopted.

Substantially High Hidden Blood Loss in Oblique Lateral Interbody Fusion: Retrospective Case Series.

: Measured blood loss frequently underestimates true blood loss; this discrepancy is called hidden blood loss (HBL). The purpose of the present study was to measure HBL in oblique lateral interbody fusion (OLIF). : Patients who underwent two-stage OLIF at our institute from September 2017 to September 2021 were retrospectively reviewed.

Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study.

Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known, each of which suffers inherent charge recombination channels that suppress the separation efficiency. We found a charge separation mechanism in the photoinduced excited-state proton transfer dynamics from Mn oxides to organic acceptors.

Gastric Myeloid Sarcoma Mimicking a Scirrhous Gastric Cancer.

Myeloid sarcoma (MS) is a relatively rare manifestation of myeloid neoplasms at sites other than the bone marrow. The rarity of gastrointestinal (GI) MS is attributed to certain factors, such as misdetection due to insufficient endoscopic assessments at the initial presentation with acute myeloid leukemia (AML) as well as the difficulty of making a histologic assessment of leukemic involvement of the GI tract. We herein report a case of AML with gastric involvement and discuss the importance of screening examinations and therapies considering the location of MS and the data of cytogenetic and molecular mutation.

An orbital picture extracted from correlated electronic wavefunctions and application to forbidden reactions: 70 years of the frontier orbital theory.

The one-electron picture in molecular electronic state theory, particularly the molecular orbital (MO) theory with the Hartree-Fock approximation, has set a foundation to develop chemical science. Frontier orbital theory, or the theory of HOMO (highest occupied MO)-LUMO (lowest unoccupied MO) interaction, and the conservation rule of orbital symmetry are among the brightest achievements in a molecular orbital picture. After 70 years from the birth of frontier orbital theory, however, electronic wavefunctions treated in current quantum chemistry are often highly correlated and consist of extensive scales of electronic configurations to be more accurate and to cope with far more complicated reactions than concerted reactions.

Dual plating for bipolar clavicle fractures: A case report.

Clavicular fractures are common, accounting for 4% of all adult fractures. However, simultaneous medial and lateral fractures occurring in the same clavicle (the so-called 'bipolar clavicle fracture') are rare. Treatment for this type of fracture is not well established.

On the molecular electronic flux: Role of nonadiabaticity and violation of conservation.

Analysis of electron flux within and in between molecules is crucial in the study of real-time dynamics of molecular electron wavepacket evolution such as those in attosecond laser chemistry and ultrafast chemical reaction dynamics. We here address two mutually correlated issues on the conservation law of molecular electronic flux, which serves as a key consistency condition for electron dynamics. The first one is about a close relation between "weak" nonadiabaticity and the electron dynamics in low-energy chemical reactions.

Energy natural orbitals.

We propose and numerically demonstrate that highly correlated electronic wavefunctions such as those of configuration interaction, the cluster expansion, and so on, and electron wavepackets superposed thereof can be analyzed in terms of one-electron functions, which we call energy natural orbitals (ENOs). As the name suggests, ENOs are members of the broad family of natural orbitals defined by Löwdin, in that they are eigenfunctions of the energy density operator. One of the major characteristics is that the (orbital) energies of all the ENOs are summed up exactly equal to the total electronic energy of a wavefunction under study.

FMD-VS: A virtual sensor to index FMD virus scattering.

Foot-and-mouth disease (FMD) models-analytical models for tracking and analyzing FMD outbreaks-are known as dominant tools for examining the spread of the disease under various conditions and assessing the effectiveness of countermeasures. There has been some remarkable progress in modeling research since the UK epidemic in 2001. Several modeling methods have been introduced, developed, and are still growing.

Charge separation and successive reconfigurations of electronic and protonic states in a water-splitting catalytic cycle with the MnCaO cluster. On the mechanism of water splitting in PSII.

Much insight into the basic mechanisms of photoexcited and collision-induced ground-state water splitting has been accumulated in our nonadiabatic electron wavepacket dynamics studies based on a building-block approach reaching up to systems of binuclear Mn oxo complexes. We here extend the study to a ground-state water-splitting catalytic cycle with tetranuclear Mn oxo complex Mn4CaO5, or Mn3Ca(H2O)2(OH)4-OH-Mn(4)(H2O)2, where Mn3Ca(H2O)2(OH)4 is fixed to a skewed cubic structure by μ-hydroxo bridges and is tied to the terminal group Mn(4)(H2O)2. We show using the method of real-time nonadiabatic electron wavepacket dynamics that four charge separation steps always take place only through the terminal group Mn(4)(H2O)2 alone, thereby producing 4 electrons and 4 protons which are transported to the acceptors.

Rapid Photoinduced Single Cell Detachment from Gold Nanoparticle-Embedded Collagen Gels with Low Denaturation Temperature.

Cell Separation is important in various biomedical fields. We have prepared gold nanoparticle (AuNP)-embedded collagen gels as a visible-light-responsive cell scaffold in which photoinduced single cell detachment occurs through local thermal denaturation of the collagen gel via the photothermal effect of AuNP. Physicochemical properties of collagen materials depend on the origin of the collagen and the presence of telopeptides.

Binuclear Mn oxo complex as a self-contained photocatalyst in water-splitting cycle: Role of additional Mn oxides as a buffer of electrons and protons.

We theoretically propose a photoinduced water-splitting cycle catalyzed by a binuclear Mn oxo complex. In our "bottom-up approach" to this problem, we once proposed a working minimal model of water-splitting cycle in terms of a mononuclear Mn oxo complex as a catalyst along with water clusters [K. Yamamoto and K.

Relativistic theory of electron-nucleus-radiation coupled dynamics in molecules: Wavepacket approach.

We propose a general theoretical scheme of relativistic electron-nucleus coupled dynamics of molecules in radiation fields, which is derived from quantum electrodynamical formalism. Aiming at applications to field-induced dynamics in ultrastrong laser pulses to the magnitude of 10 W/cm or even larger, we derive a nonperturbative formulation of relativistic dynamics using the Tamm-Dancoff expansion scheme, which results in, within the lowest order expansion, a time-dependent Schrödinger equation with the Coulombic and retarded transversal photon-exchange interactions. We also discuss a wavepacket type nuclear dynamics adapted for such dynamics.

On the Elementary Chemical Mechanisms of Unidirectional Proton Transfers: A Nonadiabatic Electron-Wavepacket Dynamics Study.

We propose a set of chemical reaction mechanisms of unidirectional proton transfers, which may possibly work as an elementary process in chemical and biological systems. Being theoretically derived based on our series of studies on charge separation dynamics in water splitting by Mn oxides, the present mechanisms have been constructed after careful exploration over the accumulated biological studies on cytochrome c oxidase (CcO) and bacteriorhodopsin. In particular, we have focused on the biochemical findings in the literature that unidirectional transfers of approximately two protons are driven by one electron passage through the reaction center (binuclear center) in CcO, whereas no such dissipative electron transfer is believed to be demanded in the proton transport in bacteriorhodopsin.