Search

We aim to perform sound event localization and detection (SELD) using wearable equipment for a moving human, such as a pedestrian. Conventional SELD tasks have dealt only with microphone arrays located in static positions. However, self-motion with three rotational and three translational degrees of freedom (6DoF) shall be considered for wearable microphone arrays. A system trained only with a dataset using microphone arrays in a fixed position would be unable to adapt to the fast relative motion of sound events associated with self-motion, resulting in the degradation of SELD performance. To address this, we designed 6DoF SELD Dataset for wearable systems, the first SELD dataset considering the self-motion of microphones. Furthermore, we proposed a multi-modal SELD system that jointly utilizes audio and motion tracking sensor signals. These sensor signals are expected to help the system find useful acoustic cues for SELD on the basis of the current self-motion state. Experimental results on our dataset show that the proposed method effectively improves SELD performance with a mechanism to extract acoustic features conditioned by sensor signals., Comment: ICASSP2024 accepted

Observations with distributed sensors are essential in analyzing a series of human and machine activities (referred to as 'events' in this paper) in complex and extensive real-world environments. This is because the information obtained from a single sensor is often missing or fragmented in such an environment; observations from multiple locations and modalities should be integrated to analyze events comprehensively. However, a learning method has yet to be established to extract joint representations that effectively combine such distributed observations. Therefore, we propose Guided Masked sELf-Distillation modeling (Guided-MELD) for inter-sensor relationship modeling. The basic idea of Guided-MELD is to learn to supplement the information from the masked sensor with information from other sensors needed to detect the event. Guided-MELD is expected to enable the system to effectively distill the fragmented or redundant target event information obtained by the sensors without being overly dependent on any specific sensors. To validate the effectiveness of the proposed method in novel tasks of distributed multimedia sensor event analysis, we recorded two new datasets that fit the problem setting: MM-Store and MM-Office. These datasets consist of human activities in a convenience store and an office, recorded using distributed cameras and microphones. Experimental results on these datasets show that the proposed Guided-MELD improves event tagging and detection performance and outperforms conventional inter-sensor relationship modeling methods. Furthermore, the proposed method performed robustly even when sensors were reduced., Comment: 13page, 7figure, under review

Surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis from carbon dioxide and methanol are suggested by means of transient spectroscopic methodologies in conjunction with multivariate spectral analysis. How the two reactants, i.e. CO2 and methanol, interact with the CeO2 surface and how they form decisive surface intermediates leading to DMC are unraveled by DFT-based molecular dynamics simulation by precise statistical sampling of various configurations of surface states and intermediates. The atomistic simulations and uncovered stability of different intermediate states perfectly explain the unique DMC formation profile experimentally observed upon transient operations, strongly supporting the proposed oxygen vacancy-assisted reaction mechanism., ChemE/Catalysis Engineering

For the fluorescence imaging of biologically active small compounds, the development of compact fluorophores that do not perturb bioactivity is required. Here we report a compact derivative of fluorescent 1,3a,6a-triazapentalenes, 2-isobutenylcarbonyl-1,3a,6a-triazapentalene (TAP-VK1), as a fluorescent labeling reagent. The reaction of TAP-VK1 with various aliphatic thiols proceeds smoothly to afford the corresponding 1,4-adducts in high yields, and nucleophiles other than thiols do not react. After the addition of thiol groups in dichloromethane, the emission maximum of TAP-VK1 shifts to a shorter wavelength and the fluorescence intensity is substantially increased. The utility of TAP-VK1 as a compact fluorescent labeling reagent is clearly demonstrated by the labeling of Captopril, which is a small molecular drug for hypertension. The successful imaging of Captopril, one of the most compact drugs, in this study demonstrates the usefulness of compact fluorophores for mechanistic studies.

There are diverse reactions including spin-state crossing, especially the reactions catalyzed by transition metal compounds. To figure out the mechanisms of such reactions, the discussion of minimum energy intersystem crossing (MEISC) points cannot be avoided. These points may be the bottleneck of the reaction or inversely accelerate the reactions by providing a better pathway. It is of great importance to reveal their role in the reactions by computationally locating the position of the MEISC points together with the reaction pathway. However, providing a proper initial guess for the structure of the MEISC point is not as easy as that of the transition state. In this work, we extended the nudged elastic band (NEB) method for multiple spin systems, which is named the multiple spin-state NEB method, and it is successfully applied to find the MEISC points while optimizing the reaction pathway. For more precisely locating the MEISC point, a revised approach was adopted. Meanwhile, our examples also suggest that special attention should be paid to the criterion to define an image optimized as the MEISC point.

There are diverse reactions including spin-state crossing, especially the reactions catalyzed by transition metal compounds. To figure out the mechanisms of such reactions, the discussion of minimum energy intersystem crossing (MEISC) points cannot be avoided. These points may be the bottleneck of the reaction or inversely accelerate the reactions by providing a better pathway. It is of great importance to reveal their role in the reactions by computationally locating the position of the MEISC points together with the reaction pathway. However, providing a proper initial guess for the structure of the MEISC point is not as easy as that of the transition state. In this work, we extended the nudged elastic band (NEB) method for multiple spin systems, which is named the multiple spin-state NEB method, and it is successfully applied to find the MEISC points while optimizing the reaction pathway. For more precisely locating the MEISC point, a revised approach was adopted. Meanwhile, our examples also suggest that special attention should be paid to the criterion to define an image optimized as the MEISC point.

In the leading order of the large-$N$ approximation, we study the renormalon ambiguity in the gluon (or, more appropriately, photon) condensate in the 2D supersymmetric $\mathbb{C}P^{N-1}$ model on~$\mathbb{R}\times S^1$ with the $\mathbb{Z}_N$ twisted boundary conditions. In our large~$N$ limit, the combination $\Lambda R$, where $\Lambda$ is the dynamical scale and $R$~is the $S^1$ radius, is kept fixed (we set $\Lambda R\ll1$ so that the perturbative expansion with respect to the coupling constant at the mass scale~$1/R$ is meaningful). We extract the perturbative part from the large-$N$ expression of the gluon condensate and obtain the corresponding Borel transform~$B(u)$. For~$\mathbb{R}\times S^1$, we find that the Borel singularity at~$u=2$, which exists in the system on the uncompactified~$\mathbb{R}^2$ and corresponds to twice the minimal bion action, disappears. Instead, an unfamiliar renormalon singularity \emph{emerges\/} at~$u=3/2$ for the compactified space~$\mathbb{R}\times S^1$. The semi-classical interpretation of this peculiar singularity is not clear because $u=3/2$ is not dividable by the minimal bion action. It appears that our observation for the system on~$\mathbb{R}\times S^1$ prompts reconsideration on the semi-classical bion picture of the infrared renormalon., Comment: 26 pages, 1 figure, the final version to appear in PTEP

In the leading order of the large-$N$ approximation, we study the renormalon ambiguity in the gluon (or, more appropriately, photon) condensate in the 2D supersymmetric $\mathbb{C}P^{N-1}$ model on~$\mathbb{R}\times S^1$ with the $\mathbb{Z}_N$ twisted boundary conditions. In our large~$N$ limit, the combination $\Lambda R$, where $\Lambda$ is the dynamical scale and $R$~is the $S^1$ radius, is kept fixed (we set $\Lambda R\ll1$ so that the perturbative expansion with respect to the coupling constant at the mass scale~$1/R$ is meaningful). We extract the perturbative part from the large-$N$ expression of the gluon condensate and obtain the corresponding Borel transform~$B(u)$. For~$\mathbb{R}\times S^1$, we find that the Borel singularity at~$u=2$, which exists in the system on the uncompactified~$\mathbb{R}^2$ and corresponds to twice the minimal bion action, disappears. Instead, an unfamiliar renormalon singularity \emph{emerges\/} at~$u=3/2$ for the compactified space~$\mathbb{R}\times S^1$. The semi-classical interpretation of this peculiar singularity is not clear because $u=3/2$ is not dividable by the minimal bion action. It appears that our observation for the system on~$\mathbb{R}\times S^1$ prompts reconsideration on the semi-classical bion picture of the infrared renormalon., Comment: 26 pages, 1 figure, the final version to appear in PTEP

In the leading order of the large-$N$ approximation, we study the renormalon ambiguity in the gluon (or, more appropriately, photon) condensate in the 2D supersymmetric $\mathbb{C}P^{N-1}$ model on~$\mathbb{R}\times S^1$ with the $\mathbb{Z}_N$ twisted boundary conditions. In our large~$N$ limit, the combination $\Lambda R$, where $\Lambda$ is the dynamical scale and $R$~is the $S^1$ radius, is kept fixed (we set $\Lambda R\ll1$ so that the perturbative expansion with respect to the coupling constant at the mass scale~$1/R$ is meaningful). We extract the perturbative part from the large-$N$ expression of the gluon condensate and obtain the corresponding Borel transform~$B(u)$. For~$\mathbb{R}\times S^1$, we find that the Borel singularity at~$u=2$, which exists in the system on the uncompactified~$\mathbb{R}^2$ and corresponds to twice the minimal bion action, disappears. Instead, an unfamiliar renormalon singularity \emph{emerges\/} at~$u=3/2$ for the compactified space~$\mathbb{R}\times S^1$. The semi-classical interpretation of this peculiar singularity is not clear because $u=3/2$ is not dividable by the minimal bion action. It appears that our observation for the system on~$\mathbb{R}\times S^1$ prompts reconsideration on the semi-classical bion picture of the infrared renormalon., Comment: 26 pages, 1 figure, the final version to appear in PTEP

In the leading order of the large-$N$ approximation, we study the renormalon ambiguity in the gluon (or, more appropriately, photon) condensate in the 2D supersymmetric $\mathbb{C}P^{N-1}$ model on~$\mathbb{R}\times S^1$ with the $\mathbb{Z}_N$ twisted boundary conditions. In our large~$N$ limit, the combination $\Lambda R$, where $\Lambda$ is the dynamical scale and $R$~is the $S^1$ radius, is kept fixed (we set $\Lambda R\ll1$ so that the perturbative expansion with respect to the coupling constant at the mass scale~$1/R$ is meaningful). We extract the perturbative part from the large-$N$ expression of the gluon condensate and obtain the corresponding Borel transform~$B(u)$. For~$\mathbb{R}\times S^1$, we find that the Borel singularity at~$u=2$, which exists in the system on the uncompactified~$\mathbb{R}^2$ and corresponds to twice the minimal bion action, disappears. Instead, an unfamiliar renormalon singularity \emph{emerges\/} at~$u=3/2$ for the compactified space~$\mathbb{R}\times S^1$. The semi-classical interpretation of this peculiar singularity is not clear because $u=3/2$ is not dividable by the minimal bion action. It appears that our observation for the system on~$\mathbb{R}\times S^1$ prompts reconsideration on the semi-classical bion picture of the infrared renormalon., Comment: 26 pages, 1 figure, the final version to appear in PTEP

We have carried out an experimental and theoretical study of CHA-zeolite supported indium (In)-oxo clusters that promote CH4 activation at room temperature. X-ray absorption fine structure (XAFS) measurements indicate the formation of multinuclear In-oxo clusters by the O-2 activation of the In(I)-exchanged CHA zeolite prepared through reductive solid-state ion exchange (RSSIE). The structure of the In-oxo clusters and their locations were investigated in detail using ab initio thermodynamic analysis. The redox properties of the In species during RSSIE and the formation of the In-oxo clusters were also studied by temperature programmed reaction and in situ XAFS measurements. The reaction of CH4 on the O-2-activated In-CHA zeolite was monitored using IR spectroscopy where adsorbed formic acid was generated at room temperature. The adsorption and C-H activation of CH4 on our plausible model of the In-oxo clusters were theoretically investigated using density functional theory calculations. We found that CH4 is likely to adsorb and react more easily on dinuclear In-oxo ions than on monomeric In-oxo ions and that the C-H bond cleavage reaction occurs via a heterolytic pathway rather than a homolytic pathway. This study reveals the potential of multinuclear In-oxo clusters as active sites for the transformation of CH4 to oxygenates under mild reaction conditions.

We have carried out an experimental and theoretical study of CHA-zeolite supported indium (In)-oxo clusters that promote CH4 activation at room temperature. X-ray absorption fine structure (XAFS) measurements indicate the formation of multinuclear In-oxo clusters by the O-2 activation of the In(I)-exchanged CHA zeolite prepared through reductive solid-state ion exchange (RSSIE). The structure of the In-oxo clusters and their locations were investigated in detail using ab initio thermodynamic analysis. The redox properties of the In species during RSSIE and the formation of the In-oxo clusters were also studied by temperature programmed reaction and in situ XAFS measurements. The reaction of CH4 on the O-2-activated In-CHA zeolite was monitored using IR spectroscopy where adsorbed formic acid was generated at room temperature. The adsorption and C-H activation of CH4 on our plausible model of the In-oxo clusters were theoretically investigated using density functional theory calculations. We found that CH4 is likely to adsorb and react more easily on dinuclear In-oxo ions than on monomeric In-oxo ions and that the C-H bond cleavage reaction occurs via a heterolytic pathway rather than a homolytic pathway. This study reveals the potential of multinuclear In-oxo clusters as active sites for the transformation of CH4 to oxygenates under mild reaction conditions.

In the leading order of the large-$N$ approximation, we study the renormalon ambiguity in the gluon (or, more appropriately, photon) condensate in the 2D supersymmetric $\mathbb{C}P^{N-1}$ model on~$\mathbb{R}\times S^1$ with the $\mathbb{Z}_N$ twisted boundary conditions. In our large~$N$ limit, the combination $\Lambda R$, where $\Lambda$ is the dynamical scale and $R$~is the $S^1$ radius, is kept fixed (we set $\Lambda R\ll1$ so that the perturbative expansion with respect to the coupling constant at the mass scale~$1/R$ is meaningful). We extract the perturbative part from the large-$N$ expression of the gluon condensate and obtain the corresponding Borel transform~$B(u)$. For~$\mathbb{R}\times S^1$, we find that the Borel singularity at~$u=2$, which exists in the system on the uncompactified~$\mathbb{R}^2$ and corresponds to twice the minimal bion action, disappears. Instead, an unfamiliar renormalon singularity \emph{emerges\/} at~$u=3/2$ for the compactified space~$\mathbb{R}\times S^1$. The semi-classical interpretation of this peculiar singularity is not clear because $u=3/2$ is not dividable by the minimal bion action. It appears that our observation for the system on~$\mathbb{R}\times S^1$ prompts reconsideration on the semi-classical bion picture of the infrared renormalon., Comment: 26 pages, 1 figure, the final version to appear in PTEP

Dioxygen binding to a model heme compound via intersystem crossing (ISC) was investigated with a multi-state multi-configurational self-consistent field method with second-order perturbation theory (MS-CASPT2) and density functional theory (DFT) calculations. In elongated Fe-O distances, the energy levels of the S-0 and T-1 states are separated, which decreases the probability of intersystem crossing in these structures. At the DFT(B97D) level of calculation, the Fe-O distances of the S-0 and T-1 states were 1.91 and 2.92 angstrom, respectively. The minimum energy intersystem crossing point (MEISCP) was located as a transition state at a Fe-O distance of 2.17 angstrom with an energy barrier of 1.0 kcal mol(-1) from the T-1 minimum. The result was verified with MS-CASPT2 calculations including the spin-orbit interaction which also showed the intersystem crossing point at a Fe-O distance of 2.05 angstrom. An energy decomposition analysis on the reaction coordinate showed the important contribution of the ring-shrinking mode of the porphyrin ring, indicating that the reaction coordinates which control the relative energy level of the spin-states play a key role in intersystem crossing.

Dioxygen binding to a model heme compound via intersystem crossing (ISC) was investigated with a multi-state multi-configurational self-consistent field method with second-order perturbation theory (MS-CASPT2) and density functional theory (DFT) calculations. In elongated Fe-O distances, the energy levels of the S-0 and T-1 states are separated, which decreases the probability of intersystem crossing in these structures. At the DFT(B97D) level of calculation, the Fe-O distances of the S-0 and T-1 states were 1.91 and 2.92 angstrom, respectively. The minimum energy intersystem crossing point (MEISCP) was located as a transition state at a Fe-O distance of 2.17 angstrom with an energy barrier of 1.0 kcal mol(-1) from the T-1 minimum. The result was verified with MS-CASPT2 calculations including the spin-orbit interaction which also showed the intersystem crossing point at a Fe-O distance of 2.05 angstrom. An energy decomposition analysis on the reaction coordinate showed the important contribution of the ring-shrinking mode of the porphyrin ring, indicating that the reaction coordinates which control the relative energy level of the spin-states play a key role in intersystem crossing.

Palau’amine has received a great deal of attention in the past two decades as an attractive synthetic target by virtue of its intriguing molecular architecture and significant immunosuppressive activity. Here we report the total synthesis of palau’amine characterized by the construction of an ABDE tetracyclic ring core including a trans-bicylo[3.3.0]octane skeleton at a middle stage of total synthesis. The ABDE tetracyclic ring core is constructed by a cascade reaction of a cleavage of the N–N bond, including simultaneous formation of imine, the addition of amide anion to the resulting imine (D-ring formation) and the condensation of pyrrole with methyl ester (B-ring formation) in a single step. The synthetic palau’amine is confirmed to exhibit excellent immunosuppressive activity. The present synthetic route has the potential to help elucidate a pharmacophore as well as the mechanistic details of immunosuppressive activity.

Experimental and theoretical studies of HXeI and HXeH molecules in Ar, Kr, and Xe matrices are presented. HXeI exhibits the H-Xe stretching bands at 1238.0 and 1239.0 cm(-1) in Ar and Kr matrices, respectively, that are blue-shifted from the HXeI band observed in a Xe matrix (1193 cm(-1)) by 45 and 46 cm(-1). These shifts are larger than those observed previously for HXeCl (27 and 16 cm(-1)) and HXeBr (37 and 23 cm(-1)); thus, the matrix effect is stronger for less stable molecules. The results for HXeI are qualitatively different from all previous results on noble-gas hydrides with respect to the frequency order between Ar and Kr matrices. For previously studied HXeCl, HXeBr, and HXeCCH, the H-Xe stretching frequency is reliably (by > 10 cm(-1)) higher in an Ar matrix than in a Kr matrix. In contrast, the H-Xe stretching frequency of HXeI in an Ar matrix is slightly lower than that in a Kr matrix. HXeH absorbs in Ar and Kr matrices at 1203.2 and 1192.1 cm(-1) (the stronger band for a Kr matrix), respectively. These bands are blue-shifted from the stronger band of HXeH in a Xe matrix (1166 cm(-1)) by 37 and 26 cm(-1), and this frequency order is the same as observed for HXeCl, HXeBr, and HXeCCH but different from HXeI. The present hybrid quantum-classical simulations successfully describe the main experimental findings. For HXeI in the < 110 > (double substitution) site, the order of the H-Xe stretching frequencies (nu(Xe) < nu(Ar) < nu(Kr)) is in accord with the experimental observations, and also the frequency shifts in Ar and Kr matrices from a Xe matrix are well predicted (30 and 34 cm(-1)). Both in the theory and experiment, the order of the H-Xe stretching frequencies differs from the case of HXeCl, which suggests the adequate theoretical description of the matrix effect. For HXeH in the < 100 > (single substitution) site, the order of the frequencies is nu(Xe) < nu(Kr) < nu(Ar), which also agrees with the experiments. The calculated

The matrix shifts of the H-Xe stretching frequency of noble-gas hydrides, HXeCCH, HXeBr, and HXeI in various noble-gas matrices (in Ne, Ar, Kr, and Xe matrices) are investigated via the hybrid quantum-classical simulations. The order of the H-Xe stretching frequencies is found to be v(gas) < v(Ne) < v(Xe) < v(Kr) < v(Ar) for HXeCCH and HXeBr, while it is v(gas) < v(Ne) < v(Xe) < v(Ar) < v(Kr) for HXeI. This order is anomalous with respect to the matrix dielectric constants, and the calculated results reproduce the experimentally observed shifts quite successfully. We also find that the matrix shifts from the gas-phase values are Delta v(HXeCCH) approximate to Delta v(HXeCl) < Delta v(HXeBr) < Delta v(HXeI) in the same noble-gas matrix environments, which implies that the weakly bound molecules exhibit large matrix shifts. The local trapping site is analyzed in detail, and it is shown that a realistic modeling of the surrounding matrix environments is essential to describe the unusual matrix shifts accurately.

Time-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys. 2013, 139, 214304). The temporal evolution of ionization energies for the excited pi pi* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the pi pi* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the n pi* state is possible at the given photon energies, but we have not found any experimental indication for signal from the n pi* state. In contrast to currently accepted relaxation mechanisms, we suggest that the n pi* state is not involved in the relaxation process of thymine in aqueous solution.

Carotenoid spheroidene (SPO) functions for photoprotection in the photosynthetic reaction centers (RCs) and effectively dissipates its triplet excitation energy. Sensitized cis-to-trans isomerization was proposed as a possible mechanism for a singlet-triplet energy crossing for the 15,15'-cis-SPO; however, it has been questioned recently. To understand the dissipative photoprotective mechanism of this important SPO and to overcome the existing controversies on this issue, we carried out a theoretical investigation using density functional theory on the possible triplet energy relaxation mechanism through the cis-to-trans isomerization. Together with the earlier experimental observations, the possible mechanism was discussed for the triplet energy relaxation of the 15,15'-cis-SPO. The result shows that complete cis-to-trans isomerization is not necessary. Twisting the C15-C15' bond leads to singlet-triplet energy crossing at phi(14,15,15',14') = 77 degrees with an energy 32.5 kJ mol(-1) (7.7 kcal mol(-1)) higher than that of the T-1 15,15'-cis minimum. Further exploration of the minimum-energy intersystem crossing (MEISC) point shows that triplet relaxation could occur at a less distorted structure (phi = 58.4 degrees) with the energy height of 26.5 KJ mol(-1) (6.3 kcal mol(-1)). Another important reaction coordinate to reach the MEISC point is the bond-length alternation. The model truncation effect, solvent effect, and spin-orbit coupling were also investigated. The singlet-triplet crossing was also investigated for the 13,14-cis stereoisomer and locked-13,14-cis-SPO. We also discussed the origin of the natural selection of the cis over trans isomer in the RC.

The matrix shifts of the H-Xe stretching frequency of noble-gas hydrides, HXeCCH, HXeBr, and HXeI in various noble-gas matrices (in Ne, Ar, Kr, and Xe matrices) are investigated via the hybrid quantum-classical simulations. The order of the H-Xe stretching frequencies is found to be v(gas) < v(Ne) < v(Xe) < v(Kr) < v(Ar) for HXeCCH and HXeBr, while it is v(gas) < v(Ne) < v(Xe) < v(Ar) < v(Kr) for HXeI. This order is anomalous with respect to the matrix dielectric constants, and the calculated results reproduce the experimentally observed shifts quite successfully. We also find that the matrix shifts from the gas-phase values are Delta v(HXeCCH) approximate to Delta v(HXeCl) < Delta v(HXeBr) < Delta v(HXeI) in the same noble-gas matrix environments, which implies that the weakly bound molecules exhibit large matrix shifts. The local trapping site is analyzed in detail, and it is shown that a realistic modeling of the surrounding matrix environments is essential to describe the unusual matrix shifts accurately.

Carotenoid spheroidene (SPO) functions for photoprotection in the photosynthetic reaction centers (RCs) and effectively dissipates its triplet excitation energy. Sensitized cis-to-trans isomerization was proposed as a possible mechanism for a singlet-triplet energy crossing for the 15,15'-cis-SPO; however, it has been questioned recently. To understand the dissipative photoprotective mechanism of this important SPO and to overcome the existing controversies on this issue, we carried out a theoretical investigation using density functional theory on the possible triplet energy relaxation mechanism through the cis-to-trans isomerization. Together with the earlier experimental observations, the possible mechanism was discussed for the triplet energy relaxation of the 15,15'-cis-SPO. The result shows that complete cis-to-trans isomerization is not necessary. Twisting the C15-C15' bond leads to singlet-triplet energy crossing at phi(14,15,15',14') = 77 degrees with an energy 32.5 kJ mol(-1) (7.7 kcal mol(-1)) higher than that of the T-1 15,15'-cis minimum. Further exploration of the minimum-energy intersystem crossing (MEISC) point shows that triplet relaxation could occur at a less distorted structure (phi = 58.4 degrees) with the energy height of 26.5 KJ mol(-1) (6.3 kcal mol(-1)). Another important reaction coordinate to reach the MEISC point is the bond-length alternation. The model truncation effect, solvent effect, and spin-orbit coupling were also investigated. The singlet-triplet crossing was also investigated for the 13,14-cis stereoisomer and locked-13,14-cis-SPO. We also discussed the origin of the natural selection of the cis over trans isomer in the RC.

Time-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys. 2013, 139, 214304). The temporal evolution of ionization energies for the excited pi pi* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the pi pi* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the n pi* state is possible at the given photon energies, but we have not found any experimental indication for signal from the n pi* state. In contrast to currently accepted relaxation mechanisms, we suggest that the n pi* state is not involved in the relaxation process of thymine in aqueous solution.

Experimental and theoretical studies of HXeI and HXeH molecules in Ar, Kr, and Xe matrices are presented. HXeI exhibits the H-Xe stretching bands at 1238.0 and 1239.0 cm(-1) in Ar and Kr matrices, respectively, that are blue-shifted from the HXeI band observed in a Xe matrix (1193 cm(-1)) by 45 and 46 cm(-1). These shifts are larger than those observed previously for HXeCl (27 and 16 cm(-1)) and HXeBr (37 and 23 cm(-1)); thus, the matrix effect is stronger for less stable molecules. The results for HXeI are qualitatively different from all previous results on noble-gas hydrides with respect to the frequency order between Ar and Kr matrices. For previously studied HXeCl, HXeBr, and HXeCCH, the H-Xe stretching frequency is reliably (by > 10 cm(-1)) higher in an Ar matrix than in a Kr matrix. In contrast, the H-Xe stretching frequency of HXeI in an Ar matrix is slightly lower than that in a Kr matrix. HXeH absorbs in Ar and Kr matrices at 1203.2 and 1192.1 cm(-1) (the stronger band for a Kr matrix), respectively. These bands are blue-shifted from the stronger band of HXeH in a Xe matrix (1166 cm(-1)) by 37 and 26 cm(-1), and this frequency order is the same as observed for HXeCl, HXeBr, and HXeCCH but different from HXeI. The present hybrid quantum-classical simulations successfully describe the main experimental findings. For HXeI in the < 110 > (double substitution) site, the order of the H-Xe stretching frequencies (nu(Xe) < nu(Ar) < nu(Kr)) is in accord with the experimental observations, and also the frequency shifts in Ar and Kr matrices from a Xe matrix are well predicted (30 and 34 cm(-1)). Both in the theory and experiment, the order of the H-Xe stretching frequencies differs from the case of HXeCl, which suggests the adequate theoretical description of the matrix effect. For HXeH in the < 100 > (single substitution) site, the order of the frequencies is nu(Xe) < nu(Kr) < nu(Ar), which also agrees with the experiments. The calculated frequency shifts for HXeH

To expand the originally developed fluorescent 1,3a,6a-triazapentalenes as fluorescent labelling reagents, the fluorescence wavelength of the 1,3a,6a-triazapentalenes was extended to the red color region. Based on the noteworthy correlation of the fluorescence wavelength with the inductive effect of the 2-substituent, electron-deficient 2-(2-cyano-4-methoxycarbonylphenyl)-1,3a,6a-triazapentalene and 2-(2,6-dicyano-4-methoxycarbonylphenyl)-1,3a,6a-triazapentalene were synthesized. The former exhibited yellow fluorescence and the latter exhibited red fluorescence, and both compounds exhibited large Stokes shifts, and the 1,3a,6a-triazapentalene system enabled the same fluorescent chromophore to cover the entire region of visible wavelengths. The potential applications of the 1,3a,6a-triazapentalenes as fluorescent probes in the fields of the life sciences were investigated, and the 1,3a,6a-triazapentalene system was clearly proven to be useful as a fluorescent reagent for live cell imaging. Quantum chemical calculations were performed to investigate the optical properties of the 1,3a,6a-triazapentalenes. These calculations revealed that the excitation involves a significant charge-transfer from the 1,3a,6a-triazapentalene skeleton to the 2-substituent. The calculated absorption and fluorescence wavelengths showed a good correlation with the experimental ones, and thus the system could enable the theoretical design of substituents with the desired optical properties.

Adsorption and catalytic activation of the molecular oxygen on the hexagonal boron nitride (h-BN) monolayer supported on Ni(111) and Cu(111) surfaces have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active on the transition metal support as a result of mixing of the metal d and h-BN pi bands.

Adsorption and catalytic activation of the molecular oxygen on the hexagonal boron nitride (h-BN) monolayer supported on Ni(111) and Cu(111) surfaces have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active on the transition metal support as a result of mixing of the metal d and h-BN pi bands.

The catalytic activity for oxygen reduction reaction (ORR) of the pristine and defected hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O2, O, OH, OOH, and H2O on N atom impurity in h-BN monolayer (N_[B]@h-BN) is quite similar to that known for Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N_[B]@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under condition that the electron transport to the catalytically active center is provided.

On-the-fly excited-state quantum mechanics/molecular mechanics molecular dynamics (QM/MM-MD) simulations of thymine in aqueous solution are performed to investigate the role of solvent water molecules on the nonradiative deactivation process. The complete active space second-order perturbation theory (CASPT2) method is employed for a thymine molecule as the QM part in order to provide a reliable description of the excited-state potential energies. It is found that, in addition to the previously reported deactivation pathway involving the twisting of the C-C double bond in the pyrimidine ring, another efficient deactivation pathway leading to conical intersections that accompanies the out-of-plane displacement of the carbonyl group is observed in aqueous solution. Decay through this pathway is not observed in the gas phase simulations, and our analysis indicates that the hydrogen bonds with solvent water molecules play a key role in stabilizing the potential energies of thymine in this additional decay pathway.

The catalytic activity for oxygen reduction reaction (ORR) of the pristine and defected hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O2, O, OH, OOH, and H2O on N atom impurity in h-BN monolayer (N_[B]@h-BN) is quite similar to that known for Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N_[B]@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under condition that the electron transport to the catalytically active center is provided.

On-the-fly excited-state quantum mechanics/molecular mechanics molecular dynamics (QM/MM-MD) simulations of thymine in aqueous solution are performed to investigate the role of solvent water molecules on the nonradiative deactivation process. The complete active space second-order perturbation theory (CASPT2) method is employed for a thymine molecule as the QM part in order to provide a reliable description of the excited-state potential energies. It is found that, in addition to the previously reported deactivation pathway involving the twisting of the C-C double bond in the pyrimidine ring, another efficient deactivation pathway leading to conical intersections that accompanies the out-of-plane displacement of the carbonyl group is observed in aqueous solution. Decay through this pathway is not observed in the gas phase simulations, and our analysis indicates that the hydrogen bonds with solvent water molecules play a key role in stabilizing the potential energies of thymine in this additional decay pathway.

We investigate the vibrational shift of beryllium oxide (BeO) in Xe matrix as well as in Ar matrix environments by mixed quantum-classical simulation and examine the origin of spectral shift in details. BeO is known to form strong chemical complex with single rare gas atom, and it is predicted from the gas phase calculations that vibrational frequencies are blueshifted by 78 cm^[-1] and 80 cm^[-1] upon formation of XeBeO and ArBeO, respectively. When the effects of other surrounding rare gas atoms are included by Monte Carlo simulations, it is found that the vibrational frequencies are redshifted by 21 cm^[-1] and 8 cm^[-1] from the isolated XeBeO and ArBeO complexes, respectively. The vibrational shift of XeBeO in Ar matrix is also calculated and compared with experimental data. In all simulations examined in this paper, the calculated vibrational frequency shifts from the isolated BeO molecule are in reasonable agreement with experimental values. The spectral shift due to the rare-gas-complex formation of RgBeO (Rg = Xe or Ar) is not negligible as seen in the previous studies, but it is shown in this paper that the effects of other surrounding rare gas atoms should be carefully taken into account for quantitative description of the spectral shifts and that these two effects are competing in vibrational spectroscopy of BeO in matrix environments.

A concept of trifurcation of a reaction pathway is introduced to analyze the case where a downhill path from the first-order saddle point accompanies three branches via the valley-ridge inflection region, leading to three different product minima on the potential energy surface. We provide a detailed analysis on the reaction path for an electron transfer reaction, HCHO- + CH3Cl → OH2C-CH3⋅⋅⋅Cl-, as an illustrative example of the trifurcating reaction path.

A concept of trifurcation of a reaction pathway is introduced to analyze the case where a downhill path from the first-order saddle point accompanies three branches via the valley-ridge inflection region, leading to three different product minima on the potential energy surface. We provide a detailed analysis on the reaction path for an electron transfer reaction, HCHO- + CH3Cl → OH2C-CH3⋅⋅⋅Cl-, as an illustrative example of the trifurcating reaction path.

We investigate the vibrational shift of beryllium oxide (BeO) in Xe matrix as well as in Ar matrix environments by mixed quantum-classical simulation and examine the origin of spectral shift in details. BeO is known to form strong chemical complex with single rare gas atom, and it is predicted from the gas phase calculations that vibrational frequencies are blueshifted by 78 cm^[-1] and 80 cm^[-1] upon formation of XeBeO and ArBeO, respectively. When the effects of other surrounding rare gas atoms are included by Monte Carlo simulations, it is found that the vibrational frequencies are redshifted by 21 cm^[-1] and 8 cm^[-1] from the isolated XeBeO and ArBeO complexes, respectively. The vibrational shift of XeBeO in Ar matrix is also calculated and compared with experimental data. In all simulations examined in this paper, the calculated vibrational frequency shifts from the isolated BeO molecule are in reasonable agreement with experimental values. The spectral shift due to the rare-gas-complex formation of RgBeO (Rg = Xe or Ar) is not negligible as seen in the previous studies, but it is shown in this paper that the effects of other surrounding rare gas atoms should be carefully taken into account for quantitative description of the spectral shifts and that these two effects are competing in vibrational spectroscopy of BeO in matrix environments.

A local thermal non-equilibrium model has been considered for the case of thermally fully developed flow within a constant heat flux tube filled with a porous medium. Exact temperature profiles for the fluid and solid phases are found after combining the two individual energy equations and then transforming them into a single ordinary differential equation with respect to the temperature difference between the solid phase and the wall subject to constant heat flux. The exact solutions for the case of metal-foam and air combination reveal that the local thermal equilibrium assumption may fail for the case of constant heat flux wall. The Nusselt number is presented as a function of the Peclet number, which shows a significant increase due to both high stagnant thermal conductivity and thermal dispersion resulting from the presence of the metal-foam.

Efficiency of the ab initio hybrid Monte Carlo and ab initio path integral hybrid Monte Carlo methods is enhanced by employing an auxiliary potential energy surface that is used to update the system configuration via molecular dynamics scheme. As a simple illustration of this method, a dual-level approach is introduced where potential energy gradients are evaluated by computationally less expensive ab initio electronic structure methods.

An approach is developed to enhance sampling for ab initioMonte Carlo and ab initio path integral Monte Carlo calculations of molecular clusters by utilizing an approximate potential as a guide to move in the configuration space more efficiently. The interpolatedpotential energy obtained by the moving least-squares method is used as an approximate potential, and this scheme is applied to a water molecule and small protonated water clusters (H3O+,H5O2+). It is found that the statistical errors are reduced by almost a factor of 3 in most calculations, which translates into a reduction in the computational cost by an order of magnitude. We also provide an automatic scheme where the ab initio data obtained during the simulation is added to the reference data set of interpolation dynamically, which further speeds up the convergence.

Efficiency of the ab initio hybrid Monte Carlo and ab initio path integral hybrid Monte Carlo methods is enhanced by employing an auxiliary potential energy surface that is used to update the system configuration via molecular dynamics scheme. As a simple illustration of this method, a dual-level approach is introduced where potential energy gradients are evaluated by computationally less expensive ab initio electronic structure methods.

An approach is developed to enhance sampling for ab initioMonte Carlo and ab initio path integral Monte Carlo calculations of molecular clusters by utilizing an approximate potential as a guide to move in the configuration space more efficiently. The interpolatedpotential energy obtained by the moving least-squares method is used as an approximate potential, and this scheme is applied to a water molecule and small protonated water clusters (H3O+,H5O2+). It is found that the statistical errors are reduced by almost a factor of 3 in most calculations, which translates into a reduction in the computational cost by an order of magnitude. We also provide an automatic scheme where the ab initio data obtained during the simulation is added to the reference data set of interpolation dynamically, which further speeds up the convergence.

Digital watermarking algorithms have been studied these days, where it is necessary and inevitable for the watermarks to be inaudible. One of the watermarking algorithms is proposed by Boney et., et al based on the MPEG psychoacoustic model. The Boney et. Watermarking algorithm uses a PN sequence as a watermark, which is passed with a zero-pole filter. In this paper, we introduce temporal masking as well as simultaneous masking and we improve the Boney et. watermarking algorithm(“First Stage” Boney et. called) on the masking approximation filter and the bandwidth for embedding the watermarks. Our approximation filter using cepstral analysis / synthesis method fitted the masking threshold much better than Boney et. one and the bandwidth for embedding the watermarks is restricted less than 12 kHz to improve the robustness against MPEG CODEC. We also introduce a self-clocking mechanism to detect the watermark automatically. The Boney et. and our watermarking algorithms are comparatively tested by a watermark detection algorithm and evaluated by objective segmental SNR and subjective tests with double blind triple stimuli tests, using several kinds of music sources. Both evaluation results show an advantage for our watermarking algorithm as follows. (1) Audio signal with embedded watermarks has no degradation and the watermarks are inaudible. (2) Our watermarking robustness against additive noise attack, low-pass filtering, resampling, MPEG encoding / decoding, DA/ AD conversion with analogue wire transmission is superior. Our watermarking can be almost detected in any cases. (3) Our watermarking algorithm is simpler than “Full Watermark Generator“ Boney et. proposed. Moreover, our watermark is inaudible and its robustness is as high as “Full Watermark Generator."

Digital watermarking algorithms have been studied these days, where it is necessary and inevitable for the watermarks to be inaudible. One of the watermarking algorithms is proposed by Boney et., et al based on the MPEG psychoacoustic model. The Boney et. Watermarking algorithm uses a PN sequence as a watermark, which is passed with a zero-pole filter. In this paper, we introduce temporal masking as well as simultaneous masking and we improve the Boney et. watermarking algorithm(“First Stage” Boney et. called) on the masking approximation filter and the bandwidth for embedding the watermarks. Our approximation filter using cepstral analysis / synthesis method fitted the masking threshold much better than Boney et. one and the bandwidth for embedding the watermarks is restricted less than 12 kHz to improve the robustness against MPEG CODEC. We also introduce a self-clocking mechanism to detect the watermark automatically. The Boney et. and our watermarking algorithms are comparatively tested by a watermark detection algorithm and evaluated by objective segmental SNR and subjective tests with double blind triple stimuli tests, using several kinds of music sources. Both evaluation results show an advantage for our watermarking algorithm as follows. (1) Audio signal with embedded watermarks has no degradation and the watermarks are inaudible. (2) Our watermarking robustness against additive noise attack, low-pass filtering, resampling, MPEG encoding / decoding, DA/ AD conversion with analogue wire transmission is superior. Our watermarking can be almost detected in any cases. (3) Our watermarking algorithm is simpler than “Full Watermark Generator“ Boney et. proposed. Moreover, our watermark is inaudible and its robustness is as high as “Full Watermark Generator.", conference paper