Photo-induced chirality switching in a cobaloxime complex crystal

Switching of molecular chirality under photo-irradiation was studied in a cobaloxime complex crystal. Excitation of the d-d transition of the Co(III) ion appeared to be much more effective in inducing the chirality change than excitation of the ligand-metal charge transfer band although the latter is more effective in breaking the Co-C bond that initiates the chirality switching. The chirality change versus irradiation time showed a steplike behavior suggesting that chirality switching of molecules occurred in correlation with their nearest neighbors.     

Second hyperpolarizability of phenalenyl radical system involving acetylene π-conjugated bridge

The static second hyperpolarizability (γ) of a singlet diradical system involving phenalenyl radicals linked with acetylene π-conjugated bridge, BPLE, is investigated as well as reference closed-shell systems, BPRY1 and BPRY2, by the hybrid density functional theory method. The γ value of BPLE with intermediate diradical character is shown to be about four times as large as that of BPRY1 with similar π-conjugation length and to be about twice as large as that of BPRY2 with longer π-conjugation length. This feature is in agreement with our prediction that the molecules with intermediate diradical characters enhance γ values compared to the closed-shell molecules.     

Intramolecular nitro-assisted proton transfer in photoirradiated 2-(2',4'-dinitrobenzyl)pyridine: polarized optical spectroscopic study and electronic structure calculations

The nitro-assisted proton transfer (NAPT), responsible for the photoactivity of ortho-nitrobenzylpyridines and a model for the nitro-based caged compounds, is studied along with the parent compound 2-(2',4'-dinitrobenzyl)pyridine (DNBP) with polarized optical spectroscopy and theoretical calculations. The transition dipole moments of a DNBP single-crystal identified oriented molecules of the long-lived enamine tautomer (NH), rather than of the aci-nitro tautomer (OH), as carriers of the photoinduced blue coloration. It is clarified that the blue second singlet transition owes to intramolecular charge transfer from the allyl-pyridinium part to the dinitrophenyl fragment of NH. The theoretical modeling of the ground-state potential energy surface showed that while NH and OH can interconvert by means of direct proton transfer, such a process between the initial form CH and either OH and NH would require significant rotation of the aromatic rings. In the ground state, OH is less stable but the kinetically preferred product over NH. Once created, regardless of whether via ground-state or excited-state routes, the aci-nitro group of OH undergoes energetically inexpensive rotation to deliver the proton to the nitrogen acceptor. The "softening" of the energy surface around OH due to its structural flexibility, that is, mediation of the proton transfer by the nitro group, is crucial to overcome the high barrier for a direct proton jump from CH to NH, even in cases of unfavorable donor-acceptor geometry. The very small structural change experienced by the surrounding of a molecule undergoing NAPT is promising for the design of photoactive systems which retain their crystallinity during a prolonged operation.     

On a unified double zeta function of Mordell–Tornheim type*

Lithuanian Mathematical Journal - We introduce a double zeta function of Mordell–Tornheim type and compute its values at nonpositive integer points. We then discuss a possible generalization...     

Existence of zero points for pseudomonotone operators in Banach spaces

The purpose of this paper is to study the existence of zero points for set-valued pseudomonotone operators in a Banach space by using a new condition which was recently proposed by the authors (Matsushita and Takahashi, Set-Valued Analysis 15:251–264, 2007).      

Strong convergence theorems for nonexpansive nonself-mappings without boundary conditions

In this paper, we study boundary conditions for nonexpansive nonself-mappings in a Banach space. Using this, we prove two strong convergence theorems for nonexpansive nonself-mappings in a Banach space without boundary conditions.     

Multiple Eisenstein series and multiple cotangent functions

We construct the multiple Eisenstein series and we show a relation to the multiple cotangent function. We calculate a limit value of the multiple Eisenstein series.     

Photoinduced phase transition of coordinationally unsaturated d9 metal centers within the thermal hysteresis of the spin exchange interaction

Diffraction evidence is presented that the structure of one-dimensional arrays of strained, coordinationally unsaturated d9 pseudo-Jahn-Teller centers is affected by excitation of the LMCT bands within the hysteresis region of the low-temperature ferromagnetic-to-antiferromagnetic phase transition.