Normal mode analysis of a relaxation process with Bayesian inference.

Measurements of relaxation processes are essential in many fields, including nonlinear optics. Relaxation processes provide many insights into atomic/molecular structures and the kinetics and mechanisms of chemical reactions. For the analysis of these processes, the extraction of modes that are specific to the phenomenon of interest (normal modes) is unavoidable. In this study we propose a framework to systematically extract normal modes from the viewpoint of model selection with Bayesian inference. Our approach consists of a well-known method called sparsity-promoting dynamic mode decomposition, which decomposes a mixture of damped oscillations, and the Bayesian model selection framework. We numerically verify the performance of our proposed method by using coherent phonon signals of a bismuth polycrystal and virtual data as typical examples of relaxation processes. Our method succeeds in extracting the normal modes even from experimental data with strong backgrounds. Moreover, the selected set of modes is robust to observation noise, and our method can estimate the level of observation noise. From these observations, our method is applicable to normal mode analysis, especially for data with strong backgrounds.

Quantifying physical insights cooperatively with exhaustive search for Bayesian spectroscopy of X-ray photoelectron spectra.

We analyzed the X-ray photoelectron spectra (XPS) of carbon 1s states in graphene and oxygen-intercalated graphene grown on SiC(0001) using Bayesian spectroscopy. To realize highly accurate spectral decomposition of the XPS spectra, we proposed a framework for discovering physical constraints from the absence of prior quantified physical knowledge, in which we designed the prior probabilities based on the found constraints and the physically required conditions. This suppresses the exchange of peak components during replica exchange Monte Carlo iterations and makes possible to decompose XPS in the case where a reliable structure model or a presumable number of components is not known. As a result, we have successfully decomposed XPS of one monolayer (1ML), two monolayers (2ML), and quasi-freestanding 2ML (qfs-2ML) graphene samples deposited on SiC substrates with the meV order precision of the binding energy, in which the posterior probability distributions of the binding energies were obtained distinguishably between the different components of buffer layer even though they are observed as hump and shoulder structures because of their overlapping.

Complex energies of the coherent longitudinal optical phonon-plasmon coupled mode according to dynamic mode decomposition analysis.

In a dissipative quantum system, we report the dynamic mode decomposition (DMD) analysis of damped oscillation signals. We used a reflection-type pump-probe method to observe time-domain signals, including the coupled modes of long-lived longitudinal optical phonons and quickly damped plasmons (LOPC) at various pump powers. The Fourier transformed spectra of the observed damped oscillation signals show broad and asymmetric modes, making it difficult to evaluate their frequencies and damping rates. We then used DMD to analyze the damped oscillation signals by precisely determining their frequencies and damping rates. We successfully identified the LOPC modes. The obtained frequencies and damping rates were shown to depend on the pump power, which implies photoexcited carrier density. We compared the pump-power dependence of the frequencies and damping rates of the LOPC modes with the carrier density dependence of the complex eigen-energies of the coupled modes by using the non-Hermitian phenomenological effective Hamiltonian. Good agreement was obtained between the observed and calculated dependences, demonstrating that DMD is an effective alternative to Fourier analysis which often fails to estimate effective damping rates.

Morphology-dependent carrier and exciton generations in regioregular poly(3-hexylthiophene) polymer diodes as revealed by bleaching spectroscopy.

Bleaching probe spectroscopy performed for regioregular poly(3-hexylthiophene) diodes reveals that coexistent morphological phases determine the conducting and optical properties of conjugated polymer films. Photoinduced absorption measurements demonstrate that exciton migration occurs from lamella aggregates to morphological sites consisting of quasiuncoupled chains and that the latter sites determine steady-state photophysical properties. Spectroscopy synchronized with diode operation reveals that the morphological locations of injected carriers in polymer diodes vary with the applied bias.

Temperature effects on quasi-isolated conjugated polymers as revealed by temperature-dependent optical spectra of 16-mer oligothiophene diluted in a sold matrix.

Temperature dependences (4-300 K) of photoluminescence (PL) and absorption spectra of 16-mer oligothiophene (16 T) extremely diluted in polypropylene (PP) have been investigated in order to clarify temperature effects on quasi-isolated conjugated polymers. The PL and absorption spectra are found to blueshift with increasing temperature. The reason for the blueshift is discussed by comparing models based on the refractive index of the solvent (PP) and on the thermal conformational change of 16 T. The blueshift is concluded to result from the thermal conformational change. Time-resolved PL spectra show a redshift of PL band following photoexcitation (spectral migration). The amount of the migration is shown to increase with increasing temperature. The increased migration is concluded to be due to the thermal conformational change. The temperature dependence of the effective conjugation length (ECL) of 16 T is calculated for the absorption and PL transitions. The calculation suggests that ECL is reduced at room temperature to two-thirds of the intrinsic chain length. The activation energy of the conformational change is estimated to be 22.4 meV from the temperature dependence of ECL. We demonstrate that the steady-state PL spectra are well reproduced by simple Franck-Condon analyses using a single Huang-Ryes factor over a wide temperature range. The analyses reveal features of temperature dependence in important spectral parameters such as the Stokes shift, linewidth, and Huang-Ryes factor.

Intrachain photoluminescence dynamics of MEH-PPV in the solid state.

The photoluminescence (PL) dynamics of poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) blended in host polymer (polypropylene, PP) matrix as well as that in the neat film has been studied. The concentration of MEH-PPV in the PP blend is designed to be fairly low (0.01 wt %) in order to observe the intrinsic intrachain PL property of MEH-PPV in the solid state. The steady-state 0-0 PL band of the blend sample shows a blue-shift of 0.12 eV with respect to that of the neat film of MEH-PPV. The PL-excitation (PLE) spectra of the blend sample exhibit definite vibronic structure, and hence we can determine the magnitude of the Stokes shift as 0.06 eV. The blend sample shows a single-exponential PL decay at 4 K with a time constant of 850 ps. We emphasize that this single-exponential-type PL decay is an intrinsic property of the intrachain PL species. Time-resolved PL measurements confirm dynamical red-shift of the PL band in the neat film, whereas this trend is not found in the case of the PP blend. These observations indicate that the energy transfer between finite segments, which can cause exciton migration, is much less efficient within the isolated MEH-PPV polymer chain compared to the case of the interchain transfer. The time-resolved measurements further demonstrate that the Stokes shift identified in the blend sample takes place at the early stage within 50 ps following photoexcitation. We attribute this Stokes shift to the rapid increase of the planarity of the MEH-PPV chain caused by the torsion of some constituent phenyl rings following photoexcitation. Finally, based on an argument on the different magnitudes of Stokes shift between the blend sample and the neat film, we conclude that the PL of MEH-PPV in the neat film predominantly occurs at the site of interchain excitations via the interchain migration of excitons.

Structure study and luminescence thermochromism in hexanuclear 6-methyl-2-pyridinethiolato copper(I) crystals.

The structure of hexanuclear 6-methyl-2-pyridinethiolato copper(I) [Cu6(6-mpyt)(6)] crystals has been studied by the X-ray diffraction analysis. These crystals show highly efficient luminescence whose color changes drastically from red to green-blue with lowering temperature from room temperature (RT) to liquid nitrogen temperature (LNT). This is a new example of luminescence thermochromism for hexanuclear copper(I) cluster compounds. Two relaxed luminescence bands appear predominantly: one (CC-band), red luminescence appearing in the lower-energy region around 1.8 eV at higher temperature, is assigned to the transition between intramolecular orbitals (MO) of a Cu cluster center (CC), and the other (CT-band), green-blue luminescence appearing at the higher energy side of 2.6 eV than the CC-band at lower temperature, is assigned to a charge transfer (CT) transition from the CC-MO to a ligand MO. Additionally, the CT band can be deconvoluted to two subbands CT(L) and CT(H). The intensities of the CC- and the CT-bands change complementarily with temperature via a thermal activation process, giving the thermochromism. All of these band shapes can be fitted by a Gaussian function, and their widths are fairly large obeying the hyperbolic cotangent law. These features reflect our system to be a strong electron-lattice coupling one. The relaxation process of the photoexcited states is discussed in terms of a configuration coordinate model.