Showing papers by "Takashi Kubo published in 2007"

Relationship between third-order nonlinear optical properties and magnetic interactions in open-shell systems: a new paradigm for nonlinear optics.

Abstract: Although most third-order nonlinear optical (NLO) materials are closed-shell singlet systems, this Letter theoretically shows that the third-order NLO properties are drastically enhanced in symmetric open-shell diradical systems with intermediate diradical character and further reveals that this enhancement is associated with the ferromagnetic and antiferromagnetic interactions. This new paradigm opens up a promising area for designing new third-order NLO materials.

Ambipolar organic field-effect transistors based on a low band gap semiconductor with balanced hole and electron mobilities

Abstract: The authors have demonstrated the thin-film properties and the ambipolar transport of a delocalized singlet biradical hydrocarbon with two phenalenyl radical moieties (Ph2-IDPL). The organic field-effect transistors (OFETs) based on Ph2-IDPL exhibit ambipolar transport with balanced hole and electron mobilities in the order of 10−3cm2∕Vs. The Ph2-IDPL film is an organic semiconductor with a low band gap of 0.8eV and has small injection barriers from gold electrodes to both the highest occupied molecular orbital and the lowest unoccupied molecular orbital. A complementary metal-oxide-semiconductor-like inverter using two identical Ph2-IDPL based ambipolar OFETs shows a sharp inversion of the input voltage with high gain.

Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: diradical character and spin multiplicity dependences.

Abstract: We have investigated the static second hyperpolarizabilities (gamma) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene pi-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the gamma values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of gamma, it turns out that the gamma values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in gamma values are not observed between the two pi-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on gamma. Changing from the singlet to the triplet state, the gamma values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of gamma is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of gamma for phenalenyl radical systems involving pi-conjugated linkers by adjusting the diradical character through the change of the linked position of pi-conjugated linkers and the spin multiplicity.

Second Hyperpolarizability of Zethrenes

Abstract: We report a study on the static second hyperpolarizabilities (γ) of zethrenes using the UBHandHLYP hybrid density functional theory method. Though zethrenes were originally considered as closed-shell systems, the values of their diradical characters, calculated from the occupation numbers of spin-unrestricted Hartree-Fock natural orbitals (UNOs), demonstrate an open-shell diradical nature, which increases with the size of the middle ring region because of the recovery of the aromaticity in that region. As references, we examine also the γ values of tetrabenzopolyacenes, which are regarded as the corresponding closed-shell systems due to their negligible diradical characters. It is found that the longitudinal γ values for zethrenes are much larger than those of the corresponding reference closed-shell systems, whereas their ratio, γ(zethrene)/γ(reference), is reduced when increasing the length of middle ring regions, i.e., when increasing the diradical character.

Finite-Field Spin-Flip Configuration Interaction Calculation of the Second Hyperpolarizabilities of Singlet Diradical Systems.

Abstract: Ab initio spin-flip configuration interaction (SF-CI) methods with the finite-field (FF) scheme are applied to the calculation of static second hyperpolarizabilities (γ) of several singlet diradical systems, i.e., the model H2 molecule under dissociation, p-quinodimethane, o-quinoid five-membered ring, and 1,4-bis(imidazole-2-ylidene)cyclohexa-2,5-diene (BI2Y) models. The SF-CI method using the UHF reference wave function provides the qualitatively correct diradical character (y) dependence of γ in a wide range of a diradical character region for H2 under dissociation and p-quinodimethane as well as o-quinoid five-membered ring models. For BI2Y, which is a real diradical system, a non-negligible spin contamination is found in the spin-unrestricted Hartree-Fock (UHF) triplet state, which results in overestimations (SF-CIS) or underestimations (SF-CIS(D)) of γ. Such deficiencies are significantly reduced when using the pure spin state, i.e., the restricted open-shell HF (ROHF) triplet wave function as the reference wave function. These results indicate the applicability of the FF-SF-CI method starting with a pure or a nearly pure high-spin state to provide qualitative or semiquantitative γ for large-size diradical systems. For selected systems, these SF-CI results are also compared to the SF equation of motion coupled cluster singles and doubles (SF-EOM-CCSD) and to SF time-dependent density functional theory (SF-TDDFT) schemes. In particular, large amounts of Hartree-Fock exchange in the functional are required to obtain qualitatively correct dependence of γ on y in the case of p-quinodimethane.

Second Hyperpolarizabilities of Singlet Polycyclic Diphenalenyl Radicals: Effects of the Nature of the Central Heterocyclic Ring and Substitution to Diphenalenyl Rings

Abstract: Adopting density functional theory and a hybrid exchange-correlation functional, the relationship between the second hyperpolarizability (γ) and the diradical character has been investigated for di...

Synthesis and characterization of acetylene-linked bisphenalenyl and metallic-like behavior in its charge-transfer complex.

Abstract: We prepared and isolated a phenalenyl-based neutral hydrocarbon (1 b) with a biradical index of 14%, as well as its charge-transfer (CT) complex 1 b-F(4)-TCNQ. The crystal structure and the small HOMO-LUMO gap assessed by electrochemical and optical methods support the singlet-biradical contribution to the ground state of the neutral 1 b. This biradical character suggests that 1 b has the electronic structure of phenalenyl radicals coupled weakly through an acetylene linker, that is, some independence of the two phenalenyl moieties. The monocationic species 1 b*+ was obtained by reaction with the organic electron acceptor F4-TCNQ. The cationic species has a small disproportionation energy deltaE for the reaction 2 x 1 b*+ 1 b + 1 b2+, which presumably originates from the independence of the phenalenyl moieties. The small deltaE led to a small on-site Coulombic repulsion U(eff) = 0.61 eV in the CT complex. Moreover, a very effective orbital overlap of the phenalenyl rings between molecules afforded a relatively large transfer integral t = 0.09 eV. The small U(eff)/4t ratio (= 1.7) resulted in a metallic-like conductive behavior at around room temperature. Below 280 K, the CT complex showed a transition into a semiconductive state as a result of bond formation between phenalenyl and F4-TCNQ carbon atoms.

Syntheses and unusual segregated-alternated hybrid stacking structure of hydrogen-bonded charge-transfer complexes composed of bis[2,3-pyridinedithiolate]metal complexes.

Abstract: We report the syntheses of new planar electron donor inorganic molecules [bis(2,3-pyridinedithiolate)metal(ll)]; [M II (Hpydt) 2 ] (M = Ni(1), Pd(2), Pt(3)) and their anions; [M II (pydt) 2 ] 2- (M = Ni(4), Pd(5)), which are equipped with both a highly lying highest occupied molecular orbital (HOMO) perpendicular to the plane and hydrogen-bonding capability in the plane. In addition, we present two novel hydrogen-bonded charge-transfer (HBCT) complexes, [M(Hpydt) 2 ]TCNQ (M = Ni, Pd), with 7,7,8,8-tetracyanoquinodimethane (TCNQ). All the neutral and ionic inorganic molecules and the HBCT complexes were successfully characterized by single-crystal X-ray crystallography. The HBCT complexes show an unusual segregated-alternated hybrid stacking structure in which each component interacts parallel to the stacks with neighboring donors and acceptors. Furthermore, the structural network is expanded as a result of a one-dimensional hydrogen-bonding chain formed between donors and acceptors perpendicular to the stacking direction. The theoretical electronic structures of the HBCT complexes are also reported.

Measurement of the B(E2,01+→21+) in the N=16 nucleus Ne26

Abstract: Differential cross section of the inelastic scattering of a 54 MeV/nucleon {sup 26}Ne beam on a lead target has been measured by detecting the deexcitation {gamma}-rays. Analysis of the first 2{sup +} state angular distribution of the inelastically scattered nuclei shows that the process cannot be considered as a pure Coulomb excitation, and nuclear contribution must be taken into account. The charge deformation deduced, {beta}{sub 2}{sup C}=0.392{+-}0.024, corresponds to a B(E2)=141{+-}18 e{sup 2} fm{sup 2} in agreement with a N=16 subshell closure.