| 1. |
Nobuki Inoue, Yoshihiro Watanabe, Haruyuki Nakano, Theoretical examination of QED Hamiltonian in relativistic molecular orbital theory, The Journal of Chemical Physics, 10.1063/5.0145577, 159, 5, 2023.08, Theoretical discussions are given on issues in relativistic molecular orbital theory to which the quantum electrodynamics (QED) Hamiltonian is applied. First, several QED Hamiltonians previously proposed are sifted by the orbital rotation invariance, the charge conjugation and time reversal invariance, and the nonrelativistic limit. The discussion on orbital rotation invariance shows that orbitals giving a stationary point of total energy should be adopted for QED Hamiltonians that are not orbital rotation invariant. A new total energy expression is then proposed, in which a counter term corresponding to the energy of the polarized vacuum is subtracted from the total energy. This expression prevents the possibility of total energy divergence due to electron correlations, stemming from the fact that the QED Hamiltonian does not conserve the number of particles. Finally, based on the Hamiltonian and energy expression, the Dirac-Hartree-Fock (DHF) and electron correlation methods are reintroduced. The QED-based DHF equation is shown to give information on positrons from negative-energy orbitals while having the same form as the conventional DHF equation. Three electron correlation methods are derived: the QED-based configuration interactions and single- and multireference perturbation methods. Numerical calculations show that the total energy of the QED Hamiltonian indeed diverged and that the counter term is effective in avoiding the divergence. The relativistic molecular orbital theory presented in this article also provides a methodology for dealing with systems containing positrons based on the QED Hamiltonian.. |
| 2. |
Yuta Kudoh, Emi Suzuki, Hikari Ochiai, Kakeru Ise, Yoshifumi Kimura, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Synthesis, Structure, and Redox and Optical Properties of 5,10,15,20‐Tetraaryl‐5‐azaporphyrinium Salts, Chemistry – A European Journal, 10.1002/chem.202302148, 2023.09, Abstract The fundamental properties of azaporphyrins can be modulated over a wide range by changing the number of meso‐nitrogen atoms. Reported herein are the first examples of 5,10,15,20‐tetraaryl‐5‐azaporphyrinium (MTAMAP) salts, which were prepared via metal‐templated cyclization of the corresponding zinc(II) and copper(II) complexes of 10‐aryl‐1‐chloro‐19‐benzoyl‐5,15‐dimesityl‐10‐azabiladiene‐ac. The inclusion of one meso‐nitrogen atom in the 5,10,15,20‐tetraarylporphyrin skeleton considerably changes the redox and optical properties as well as the degree of aromaticity of the porphyrin ring. The present findings suggest that MTAMAP salts would be promising scaffolds for the development of new azaporphyrin‐based ionic fluorophores and photosensitizers. . |
| 3. |
Akane Umemiya, Haruyuki Nakano, Nanami Iwaya, Tadaaki Ikoma, Yoshihiro Matano, Synthesis and optical properties of 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins, Journal of Porphyrins and Phthalocyanines, 10.1142/s1088424623500840, A-L, 2023.06, Singlet–singlet and triplet-triplet energy-transfer processes between anthracenes and porphyrins have received considerable attention in materials chemistry. Herein, we report the first examples of 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins (BPABPs) designed to study intramolecular energy transfer between two chromophores. The Curtius rearrangement of 3,5-bis(10-phenylanthracen-9-yl)benzoyl azide in the presence of the platinum(II) complex of 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-hydroxyphenyl)porphyrin or its free base in toluene afforded the corresponding BPABP. Spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the anthracene and porphyrin [Formula: see text]-electron systems of the BPABPs are not conjugated and consequently do not affect each other’s absorption properties. In contrast, the BPABPs exhibited considerably different luminescence properties to those of phenyl 3,5-bis(10-phenylanthracen-9-yl)carbamate and 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-methoxyphenyl)porphyrins; the anthracene units of the BPABPs show considerably quenched fluorescence compared to that of the reference anthracene, indicative of efficient intramolecular singlet–singlet energy transfer from the anthracene to the porphyrin unit. The phosphorescence quantum yield of the Pt complex of BPABP is comparable to that of the reference Pt-porphyrin, which suggests that intramolecular triplet-triplet energy transfer from the Pt-porphyrin to the anthracene unit is inefficient. The present findings improve our understanding of how structural factors and excited-state energy levels affect energy transfer and triplet-triplet annihilation upconversion processes of covalently linked bisanthracene-appended porphyrins. . |
| 4. |
Natthiti Chiangraeng, Haruyuki Nakano, Piyarat Nimmanpipug, Norio Yoshida, Selective molecular recognition of amino acids and their derivatives by cucurbiturils in aqueous solution: An MD/3D-RISM study, Journal of Molecular Liquids, 10.1016/j.molliq.2023.122503, 386, 122503-122503, 2023.09. |
| 5. |
Aotake, T., Suzuki, M., Aratani, N., Yuasa, J., Kuzuhara, D., Hayashi, H., Nakano, H., Kawai, T., Wu, J., Yamada, H., 9,9′-Anthryl-anthroxyl radicals: Strategic stabilization of highly reactive phenoxyl radicals, Chemical Communications, 10.1039/c4cc10104a, 51, 31, 6734-6737, 2015.02, Stable 9,9'-anthryl-anthroxyl radicals were synthesized and isolated, and the structures were fully characterized by single crystal X-ray diffraction analysis and ESR measurement. The resonance structure and steric protection of the peripheral positions and the most reactive 9-position of anthracene prolong the half-life of the radical in solution to 11 days.. |
| 6. |
Kawashima, Y., Nakano, H., Jung, J., Ten-Nod, S., A combined quantum mechanical and molecular mechanical method using modified generalized hybrid orbitals: Implementation for electronic excited states, Physical Chemistry Chemical Physics, 10.1039/c1cp20438f, 13, 24, 11731-11738, 2011.05, The generalized hybrid orbital (GHO) method is implemented at the second-order approximate coupled cluster singles and doubles (CC2) level for quantum mechanical (QM)/molecular mechanical (MM) electronic excited state calculations. The linear response function of CC2 in the GHO scheme is derived and implemented. The new implementation is applied to the first singlet excited states of three aromatic amino acids, phenylalanine, tyrosine, and tryptophan, and also bacteriorhodopsin for assessment. The results obtained for aromatic amino acids agreed well with the full QM CC2 calculations, while the calculated excitation energies of bacteriorhodopsin and its chromophore, all-trans retinal, reproduced the environmental shift of the experimental data. For the bacteriorhodopsin case, the environmental shift of GHO also showed good agreements with the experimental data. The contribution of the quantum effect of certain moieties in the excited states is elucidated by changing the partitioning of QM and MM regions.. |
| 7. |
Shoichi Tanimoto, Koichi Tamura, Shigehiko Hayashi, Norio Yoshida, Haruyuki Nakano, A computational method to simulate global conformational changes of proteins induced by cosolvent, Journal of Computational Chemistry, 10.1002/jcc.26481, 42, 8, 552-563, 2021.03, A computational method to investigate the global conformational change of a protein is proposed by combining the linear response path following (LRPF) method and three-dimensional reference interaction site model (3D-RISM) theory, which is referred to as the LRPF/3D-RISM method. The proposed method makes it possible to efficiently simulate protein conformational changes caused by either solutions of varying concentrations or the presence of cosolvent species by taking advantage of the LRPF and 3D-RISM. The proposed method is applied to the urea-induced denaturation of ubiquitin. The LRPF/3D-RISM trajectories successfully simulate the early stage of the denaturation process within the simulation time of 300 ns, whereas no significant structural change is observed even in the 1 μs standard MD simulation. The obtained LRPF/3D-RISM trajectories reproduce the mechanism of the urea denaturation of ubiquitin reported in previous studies, and demonstrate the high efficiency of the method.. |
| 8. |
Fujiki, Ryo, Kasai, Yukako, Seno, Yuki, Matsui, Toru, Shigeta, Yasuteru, Yoshida, Norio, Nakano, Haruyuki, A computational scheme of pK values based on the three-dimensional reference interaction site model self-consistent field theory coupled with the linear fitting correction scheme, Physical chemistry chemical physics : PCCP, 10.1039/c8cp04354j, 20, 43, 27272-27279, 2018.08, A scheme for quantitatively computing the acid dissociation constant, pKa, of hydrated molecules is proposed. It is based on the three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) theory coupled with the linear fitting correction (LFC) scheme. In LFC/3D-RISM-SCF, pKa values of target molecules are evaluated using the Gibbs energy difference between the protonated and unprotonated states calculated by 3D-RISM-SCF and the parameters fitted by the LFC scheme to the experimental values of training set systems. The pKa values computed by LFC/3D-RISM-SCF show quantitative agreement with the experimental data.. |
| 9. |
Ryo Fujiki, Yukako Kasai, Yuki Seno, Toru Matsui, Yasuteru Shigeta, Norio Yoshida, Haruyuki Nakano, A computational scheme of pKa values based on the three-dimensional reference interaction site model self-consistent field theory coupled with the linear fitting correction scheme, Physical Chemistry Chemical Physics, 10.1039/C8CP04354J, 20, 43, 27272-27279, 2018.08, A scheme for quantitatively computing the acid dissociation constant, pK , of hydrated molecules is proposed. It is based on the three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) theory coupled with the linear fitting correction (LFC) scheme. In LFC/3D-RISM-SCF, pK values of target molecules are evaluated using the Gibbs energy difference between the protonated and unprotonated states calculated by 3D-RISM-SCF and the parameters fitted by the LFC scheme to the experimental values of training set systems. The pK values computed by LFC/3D-RISM-SCF show quantitative agreement with the experimental data. a a a. |
| 10. |
Satoshi Omomo, Yukihiro Tsuji, Kenichi Sugiura, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, Yoshihiro Matano, Back Cover: Unsymmetrically Substituted Donor-π-Acceptor-Type 5,15-Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties (ChemPlusChem 5/2017), ChemPlusChem, 10.1002/cplu.201700119, 82, 5, 695-704, 2017.05. |
| 11. |
Satoshi Omomo, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano, Comparison of electronic effects of β-aryl substituents on optical and electrochemical properties of 5,15-diazaporphyrin π-systems, Journal of Porphyrins and Phthalocyanines, 10.1142/s1088424615500509, 19, 06, 775-785, 2015.06, The syntheses and optical/electrochemical properties of 3-aryl-10,20-dimesityl-5,15-diazaporphyrin-metal complexes (MDAPs; mesityl = 2,4,6-trimethylphenyl; M = Ni , Zn ) are reported. Treatment of 3-bromo-MDAPs with arylboronic acids in the presence of a Pd catalyst and a bulky phosphine ligand in a dioxane-water mixed solvent afforded the corresponding 3-aryl-MDAPs in moderate to good yields. X-ray crystallographic analysis of p- EtO 2 CC 6 H 4- NiDAP showed that the β-aryl group was tilted toward the NiDAP ring, with a dihedral angle of 21.7°. In the UV-visible absorption spectra, all the Ar-MDAPs showed intense Q-bands attributable to HOMO-to-LUMO transitions. The para substituents were found to influence the HOMO energies, which eventually resulted in fine tuning of the HOMO–LUMO gaps of the diazaporphyrin chromophores. It is worth noting that the p- Ph 2 NC 6 H 4- ZnDAP showed broad absorption and emission bands in the visible-near-infrared regions. The large Stokes shifts and their linear solvation energy relationships vs. orientation polarizability show that this Ph 2 N -substituted derivative has intrinsically high charge transfer from the triphenylamine (donor) to the ZnDAP (acceptor) unit. These experimental observations were supported by theoretical calculations for model Ar-ZnDAP compounds. These results confirm that the introduction of a highly electron-donating aryl group at the peripheral β-carbon is a promising strategy for enhancing the light-harvesting and light-emitting abilities of diazaporphyrin-based π-systems in the visible-near-infrared regions.. |
| 12. |
Hikari Ochiai, Tomoaki Miura, Tadaaki Ikoma, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Copper(II) Complexes of 10,20-Diaryl-5,15-diazaporphyrin: Alternative Synthesis, Excited State Dynamics, and Substituent Effect on the 1O2-Generation Efficiency, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.20220002, 95, 3, 427-432, 2022.03, The synthesis, excited state dynamics, and substituent effect on the 1O2-generation efficiency of several copper(II) complexes of 5,15-diazaporphyrin (CuDAPs) bearing peripheral substituents are reported. 10,20-Diaryl-CuDAPs were prepared via a new method consisting of metal-templated cyclization and N-dealkylation as key steps. The effect of the β-substituents on the optical and redox properties of CuDAP was stronger than that of the meso-aryl groups, which can be explained by considering the characteristics of the HOMO and LUMO of the DAP ring. The excited state dynamics and 1O2-generation efficiency of CuDAPs were studied using time-resolved spectroscopic techniques; the electronic effect of the meso-aryl groups on the triplet lifetime and 1O2-generation quantum yield was relatively weak, whereas that of the β-(1-pyrazolyl) groups was appreciable. The analysis of the temperature dependence of phosphorescence spectra of 10,20-bis(2,4,6-trimethylphenyl)-CuDAP allowed the energy gap between the excited trip-quartet and trip-doublet states to be determined. The relatively long triplet lifetimes of CuDAPs show their potential for future application as photosensitizers.. |
| 13. |
Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers, Angewandte Chemie International Edition, 10.1002/anie.201800471, 57, 14, 3797-3800, 2018.03. |
| 14. |
Nirun Ruankaew, Norio Yoshida, Yoshihiro Watanabe, Akira Nakayama, Haruyuki Nakano, Saree Phongphanphanee, Distinct ionic adsorption sites in defective Prussian blue: a 3D-RISM study, Physical Chemistry Chemical Physics, 10.1039/C9CP04355A, 21, 40, 22569-22576, 2019.09, Ferric hexacyanoferrate (FeHCF) or Prussian blue (PB) exhibits selective alkali ion adsorption and has great potential for use in various applications. In the present work, alkali ion (Li , Na , K , and Cs ) and water configurations in defective PB (d-PB) were studied by using the statistical mechanics of molecular liquids. The three-dimensional (3D) distribution functions of the ions and water were determined by solving the 3D-reference interaction site model (RISM) equation of systems of a unit lattice of d-PB in electrolyte solutions, i.e., LiCl, NaCl, KCl, and CsCl. The results show the difference in the ion-water configurations and distributions between small (Li and Na ) and large ions (K and Cs ). The adsorption sites of Li and Na are located off-center and lie on the diagonal axis. By contrast, the larger ions, K and Cs , are adsorbed at the center of the unit cell. The degree of dehydration due to the adsorption of alkali ions indicates that there was no water exchange during Li and Na adsorption, whereas two and three water molecules were removed after adsorption of K or Cs in the unit cell. + + + + + + + + + + + + + + + +. |
| 15. |
Shoichi Tanimoto, Norio Yoshida, Tsuyoshi Yamaguchi, Seiichiro L. Ten-no, Haruyuki Nakano, Effect of Molecular Orientational Correlations on Solvation Free Energy Computed by Reference Interaction Site Model Theory, Journal of Chemical Information and Modeling, 10.1021/acs.jcim.9b00330, 59, 9, 3770-3781, 2019.09, The effect of molecular orientational correlations on the solvation free energy (SFE) of one-dimensional and three-dimensional reference interaction site models (1D- and 3D-RISM) is investigated. The repulsive bridge correction (RBC) and the partial wave (PW) expansion are representative approaches for accounting for the orientational correlation partially lacking in original 1D- and 3D-RISM. The SFEs of 1D- and 3D-RISM for a set of small organic molecules are compared with the simulation results. Accordingly, the SFE expressions, based on RBC and PW, provide more accurate results than those of the uncorrected HNC or KH SFE expressions, which indicates that accounting for molecular orientational dependencies significantly contributes to the improvement of the SFE. The SFE component analysis indicates that the nonpolar component mainly contributes to the correction. The dependence of the error in the RISM SFE on the number of solute sites is examined. In addition, we discuss the differences between 1D- and 3D-RISM through the effect of these corrections.. |
| 16. |
Sato, H., Uno, H., Nakano, H., Identification of geometrical isomers using vibrational circular dichroism spectroscopy: A series of mixed-ligand complexes of diamagnetic Co(III) ions, Dalton Transactions, 10.1039/c0dt01342k, 40, 6, 1332-1337, 2011.01, Vibrational circular dichroism (VCD) spectra were measured on the chloroform solutions of a series of mixed-ligand diamagnetic Co(III) complexes, [Co(tfac)(n)(acac)(3-n)] (n = 0-3, tfac = 1,1,1-trifluoro-2,4-pentanedionato; acac = acetylacetonato). Distinct differences were observed in the VCD spectra among the geometrical isomers of the same ligand composition. Such differentiation was hardly possible by their infra-red spectra alone. The structural identification of these isomers was performed in conjunction with DFT calculations.. |
| 17. |
Norio Yoshida, Tsuyoshi Yamaguchi, Haruyuki Nakano, Implementation of solvent polarization in three-dimensional reference interaction-site model self-consistent field theory, Chemical Physics Letters, 10.1016/j.cplett.2022.139579, 797, 139579-139579, 2022.06, The three-dimensional reference interaction-site model self-consistent field (3D-RISM-SCF) theory is an electronic structure theory of solvated molecules, which can handle the electronic polarization of the solute molecule induced by the interaction with the solvent, whereas the electronic polarization of solvent molecules is ignored. Here, the solvent-polarizable model is implemented to take into account the electronic polarization of solvent molecules. It is applied to the water molecule in an aqueous solution and the p-nitroaniline molecule in an aqueous solution, and the effects of the solvent polarization on the properties of these solutes are demonstrated.. |
| 18. |
Daisuke Okamoto, Yoshihiro Watanabe, Norio Yoshida, Haruyuki Nakano, Implementation of state-averaged MCSCF method to RISM- and 3D-RISM-SCF schemes, Chemical Physics Letters, 10.1016/j.cplett.2019.05.051, 730, 179-185, 2019.09, The state-averaged multiconfiguration self-consistent field (MCSCF) method was implemented to the reference interaction site model and three-dimensional reference interaction site model (RISM and 3D-RISM) SCF schemes, where the electronic structures of multiple states and solvation structure are determined simultaneously by the state-averaged MCSCF method and state-specific RISM-SCF/3D-RISM-SCF scheme, respectively, in a single calculation. The method was applied to the potential energy curves of the low-lying states of NaCl in aqueous solution and solvation shifts of the excitation energy of formaldehyde and p-nitroaniline. The results showed good agreement with those of the state-specific MCSCF and/or experiments.. |
| 19. |
Sakata, T., Kawashima, Y., Nakano, H., Low-lying excited states of 7-aminocoumarin derivatives: A theoretical study, International Journal of Quantum Chemistry, 10.1002/qua.22019, 109, 9, 1940-1949, 2009.03, Excited states of three 7-aminocoumarin derivatives, coumarin 120 (7-amino-4-methylcoumarin), pyrrolyl coumarin 7-(1H-pyrrol-1-yl)-4-methyl-2H-1-benzopyran-2-one, and carbazole-coumarin hybrid 10H-4-methyl-2H-2-oxopyrano[5,6-b]carbazole, have been studied using B3LYP time-dependent density functional theory (TDDFT). The solvent effect has been taken Into account using the polarizable continuum model. The spectra calculated using TDDFT agree well with the experimental absorption spectra. The electronic structures and the solvent effect for the low-lying singlet excited states have been investigated. The HOMO of the pyrrolyl coumarin is localized on the pyrrolyl ring, while the HOMO in the other 7-aminocoumarins is delocalized over the entire molecule. This leads to the weak fluorescence of the pyrrolyl coumarins found in experiments. The HOMO and next HOMO in carbazole-coumarin hybrids have similar orbital energy values, which is not the case in the other 7-aminocoumarin derivatives. This leads to the additional peaks found in the 30,000-40,000 cm(-1) region of the observed absorption spectra, which are specific for carbazole-coumarin hybrids. (c) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1940-1949, 2009. |
| 20. |
Moriyama, H., Tatewaki, H., Watanabe, Y., Nakano, H., Molecular spinors suitable for four-component relativistic correlation calculations: Studies of LaF+ and LaF using multiconfigurational quasi-degenerate perturbation theory, International Journal of Quantum Chemistry, 10.1002/qua.22013, 109, 9, 1898-1904, 2009.02, Multiconfigurational second-order quasidegenerate perturbation theory (MCQDPT) calculations were performed for the LaF+ molecule, with one LaF2+ and four LaF+ Dirac-Fock-Roothaan (DFR) spinor sets. The best spinor set was that of LaF2+, which gave the lowest total energies and also the best excitation energies for any state considered. The MCQDPT calculations with the cation and neutral molecular spinors were also performed for LaF. The MCQDPT with the cation spinors gave the lowest total energies for all states under consideration, and the calculated excitation energies compared best with experiment. We prefer the LaF+ spinor set to those of LaF. These calculations indicate that the DFR spinor set for the (n-1) electron system is adequate for treating the molecular electronic system having n electrons. (c) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1898-1904, 2009. |
| 21. |
Yoshihiro Matano, Makoto Nakashima, Takashi Nakabuchi, Hiroshi Imahori, Shinya Fujishige, Haruyuki Nakano, Monophosohaporphyrins: Oxidative π-Extension at the Peripherally-Fused Carbocycle of the Phosphaporphyrin Ring, Organic Letters, 10.1021/ol7029118, 10, 4, 553-556, 2008.02. |
| 22. |
Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, Yoshihiro Matano, Nitrogen-Bridged Metallodiazaporphyrin Dimers: Synergistic Effects of Nitrogen Bridges and meso -Nitrogen Atoms on Structure and Properties, Chemistry - An Asian Journal, 10.1002/asia.201700204, 12, 7, 816-821, 2017.04, NH-bridged and pyrazine-fused metallodiazaporphyrin dimers have been prepared from nickel(II) and copper(II) complexes of 3-amino-5,15-diazaporphyrin by Pd-catalyzed C−N cross-coupling and oxidative dimerization reactions, respectively. The synergistic effects of the nitrogen bridges and meso-nitrogen atoms play major roles in enhancing the light-harvesting properties and delocalization of an electron spin over the entire π-skeletons of the metallodiazaporphyrin dimers.. |
| 23. |
Ryo Fujiki, Toru Matsui, Yasuteru Shigeta, Haruyuki Nakano, Norio Yoshida, Recent Developments of Computational Methods for pKa Prediction Based on Electronic Structure Theory with Solvation Models, J, 10.3390/j4040058, 4, 4, 849-864, 2021.12, The protonation/deprotonation reaction is one of the most fundamental processes in solutions and biological systems. Compounds with dissociative functional groups change their charge states by protonation/deprotonation. This change not only significantly alters the physical properties of a compound itself, but also has a profound effect on the surrounding molecules. In this paper, we review our recent developments of the methods for predicting the Ka, the equilibrium constant for protonation reactions or acid dissociation reactions. The pKa, which is a logarithm of Ka, is proportional to the reaction Gibbs energy of the protonation reaction, and the reaction free energy can be determined by electronic structure calculations with solvation models. The charge of the compound changes before and after protonation; therefore, the solvent effect plays an important role in determining the reaction Gibbs energy. Here, we review two solvation models: the continuum model, and the integral equation theory of molecular liquids. Furthermore, the reaction Gibbs energy calculations for the protonation reactions require special attention to the handling of dissociated protons. An efficient method for handling the free energy of dissociated protons will also be reviewed. . |
| 24. |
Nakano, H., Nakajima, T., Tsuneda, T., Hirao, K., Recent advances in ab initio, density functional theory, and relativistic electronic structure theory, Theory and Applications of Computational Chemistry, 10.1016/B978-044451719-7/50063-9, 507-557, 2005.01, This chapter focuses on development of abinitio multireference-based perturbation theory, exchange and correlation functionals in density functional theory, and molecular theory including relativistic effects. The new developed methodologies in quantum chemistry, particularly the multireference-based perturbation theory for describing chemical reactions and excited states, relativistic molecular theory to treat heavy elements, parameter-free (less) and long-range corrected (LC) exchange and correlation functionals in density functional theory, highly efficient algorithms for calculating molecular integrals over generally contracted Gaussians, etc. UTCHEM is a research product of work to develop new and better theoretical methods in quantum chemistry. Most of the codes have been developed recently by Hirao's group at the University of Tokyo. The basic philosophy behind UTCHEM is to develop methods that allow an accurate and efficient computational chemistry of electronic structure problems for molecular systems in both the ground and excited states. UTCHEM also contains codes for well-developed methods such as MPn, CI, and CC, etc., which are standard in most quantum chemistry programs. © 2005 Elsevier B.V. All rights reserved.. |
| 25. |
Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano, Redox switchable 19 π and 18 π 5,10,20-triaryl-5,15-diazaporphyrinoid-nickel(II) complexes, Journal of Porphyrins and Phthalocyanines, 10.1142/S1088424618500529, 22, 7, 542-551, 2018.07, The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)-bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the N-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18π (cation) and 19π (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP π-system. NMR spectroscopy of the 18π TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19π TriADAP showed a highly delocalized electron spin of the π-radical. The para substituents of the N-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic β-protons observed in the 1H NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18π-19π redox-switchable optical and magnetic properties.. |
| 26. |
Nobuki Inoue, Yoshihiro Watanabe, Haruyuki Nakano, Relativistic two-electron repulsion operator formulas for the Douglas–Kroll method, Chemical Physics Letters, 10.1016/j.cplett.2020.138158, 762, 138158-138158, 2021.01, Two-electron repulsion operator formulas for the second- and third-order Douglas–Kroll (DK2 and DK3) method were derived and implemented. The formulas were applied to helium-like ions with Z = 10, 20, …, 130, and to rare gas atoms. The energies obtained for the DK2 and DK3 two-electron operators showed differences from the four-component method that were one order of magnitude smaller than those of the nonrelativistic and DK1 two-electron operators. Approximation formulas for the small component-type two-electron integrals were also derived; they were applied to the helium-like ions with Z = 80 and 130 and were numerically confirmed to reproduce unapproximated values very accurately.. |
| 27. |
Nirun Ruankaew, Norio Yoshida, Yoshihiro Watanabe, Haruyuki Nakano, Saree Phongphanphanee, Size-dependent adsorption sites in a Prussian blue nanoparticle: A 3D-RISM study, Chemical Physics Letters, 10.1016/j.cplett.2017.06.053, 684, 117-125, 2017.09, The specific adsorption of alkali ions, Li , Na , K , and Cs , in electrolyte solutions on Prussian blue (PB) is investigated by using the three-dimensional (3D) reference interaction site-model (RISM) theory. The results from 3D-RISM show dramatically different adsorption sites between large ions (K and Cs ) and small ions (Li and Na ). The small ions are adsorbed at the channel entrance sites without the water–ion exchange mechanism. In contrast, the large ions are adsorbed in PB by the water–ion exchange mechanism, and the adsorption site of large ions is located at the center of the cage or at the interstitial site. + + + + + + + +. |
| 28. |
Yuichi Tanaka, Yukio Kawashima, Norio Yoshida, Haruyuki Nakano, Solvatochromism and preferential solvation of Brooker's merocyanine in water-methanol mixtures, Journal of Computational Chemistry, 10.1002/jcc.24902, 38, 28, 2411-2419, 2017.10, The excitation energy of Brooker's merocyanine in water–methanol mixtures shows nonlinear behavior with respect to the mole fraction of methanol, and it was suggested that this behavior is related to preferential solvation by methanol. We investigated the origin of this behavior and its relation to preferential solvation using the three-dimensional reference interaction site model self-consistent field method and time-dependent density functional theory. The calculated excitation energies were in good agreement with the experimental behavior. Analysis of the coordination numbers revealed preferential solvation by methanol. The free energy component analysis implied that solvent reorganization and solvation entropy drive the preferential solvation by methanol, while the direct solute–solvent interaction promotes solvation by water. The difference in the preferential solvation effect on the ground and excited states causes the nonlinear excitation energy shift. © 2017 Wiley Periodicals, Inc.. |
| 29. |
Jun-Ichi Saito, Kuniaki Ara, Ken-Ichiro Sugiyama, Hiroshi Kitagawa, Haruyuki Nakano, Kan Ogata, Naoki Yoshioka, Study on Chemical Reactivity Control of Liquid Sodium: Development of Nano-Fluid and Its Property and Applicability to FBR Plant, Volume 1: Plant Operations, Maintenance, Installations and Life Cycle; Component Reliability and Materials Issues; Advanced Applications of Nuclear Technology; Codes, Standards, Licensing and Regulatory Issues, 10.1115/icone16-48367, 1, 559-563, 2008.01, Liquid sodium is used as the coolant of the fast breeder reactor (FBR). A weak point of sodium is a high chemical reactivity with water or oxygen. So an idea of chemical reactivity suppression of liquid sodium itself is proposed. The idea is that nano-meter size particles (hereafter called nano-particles) are dispersed in liquid sodium, and an atomic interaction which is generated between nano-particle and sodium atoms is applied to suppress the chemical reactivity. We call sodium that has dispersed the nano-particle a Nano-fluid. Three key technologies which are the trial manufacture of Nano-fluid, the reaction property of the Nano-fluid and applicability of Nano-fluid to FBR Plant have been carried out to develop the Nano-fluid.. |
| 30. |
Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20π, 19π, and 18π 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids, Chemistry-A European Journal, 10.1002/chem.201703664, 23, 64, 16364-16373, 2017.11. |
| 31. |
Fawzi Abou-Chahine, Daisuke Fujii, Hiroshi Imahori, Haruyuki Nakano, Nikolai V. Tkachenko, Yoshihiro Matano, Helge Lemmetyinen, Synthesis and Photophysical Properties of Two Diazaporphyrin–Porphyrin Hetero Dimers in Polar and Non-Polar Solutions, The Journal of Physical Chemistry B, 10.1021/jp510903a, 119, 24, 7328-7337, 2015.06. |
| 32. |
Keisuke Sudoh, Ko Furukawa, Haruyuki Nakano, Soji Shimizu, Yoshihiro Matano, Synthesis and properties of redox-switchable zinc complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin, Heteroatom Chemistry, 10.1002/hc.21456, 29, 5-6, e21456, 2018.12, The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin (TriAAOP) were investigated. Metal-templated cyclization of a zinc(II) 1,19-dichloro-5,10,15-triaryl-10-azatetrapyrrin complex with an oxygen source afforded 20π TriAAOP in the neutral form. Oxidation of 20π TriAAOP with silver (I) hexafluorophosphate generated the 19π radical cation or 18π dication depending on the content of oxidant used. The interconversion between the three oxidation states (18π, 19π, and 20π) resulted in distinct changes in the aromaticity and optical properties of the 15-aza-5-oxaporphyrin π-system. Nuclear magnetic resonance spectroscopy of 20π TriAAOP revealed its antiaromatic character, whereas that of the 18π TriAAOP dication showed its aromatic character. The combined effect of the two meso-heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20-tetraaryl-5,15-diaz-aporphyrin (TADAP). In the ultraviolet-visible-near–infrared spectra of the materials, the lowest-energy electronic excitations of the 19π and 18π TriAAOP derivatives were considerably red-shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP π-systems were energetically stabilized relative to those of the TADAP π-system. The present findings corroborate that the meso-modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light-response properties that are switchable by reversible single electron transfer processes.. |
| 33. |
Mai Mutoh, Keisuke Sudoh, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano, Synthesis of Redox-switchable 5,15-Dialkyl-10,20-diaryl-5,15-diazaporphyrins and Diversification of their N-Alkyl Groups, Asian Journal of Organic Chemistry, 10.1002/ajoc.201900085, 8, 3, 352-355, 2019.03, Nickel(II) and copper(II) complexes of redox-switchable 20π, 19π, and 18π 5,15-dialkyl-10,20-diaryl-5,15-diazaporphyrins were prepared through a metal-templated cyclization method. Furthermore, the terminal silyloxy groups in the peripheral N-alkyl chains were transformed into hydroxy groups by deprotection. It is worth noting that redox reactions between the 19π and 18π systems bearing hydroxy groups caused a change in the water solubility of the diazaporphyrin chromophore.. |
| 34. |
Chen Yang, Yoshihiro Watanabe, Norio Yoshida, Haruyuki Nakano, Three-Dimensional Reference Interaction Site Model Self-Consistent Field Study on the Coordination Structure and Excitation Spectra of Cu(II)–Water Complexes in Aqueous Solution, The Journal of Physical Chemistry A, 10.1021/acs.jpca.9b01364, 123, 15, 3344-3354, 2019.04. |
| 35. |
Satoshi Omomo, Yukihiro Tsuji, Kenichi Sugiura, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, Yoshihiro Matano, Unsymmetrically Substituted Donor-π-Acceptor-Type 5,15-Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties, ChemPlusChem, 10.1002/cplu.201700051, 82, 5, 695-704, 2017.05. |
| 36. |
21aAF-5 Theoretical prediction of pKa values of amino acids using 3D-RISM-SCF. |
