Nobuyuki Akai

Relationship between the Broad OH Stretching Band of Methanol and Hydrogen-Bonding Patterns in the Liquid Phase

The OH stretching (nu(OH)) band of methanol observed in condensed phase has been analyzed in terms of hydrogen-bonding patterns. Quantum chemical calculations for methanol clusters have revealed that broadening of the nu(OH) envelope is reasonably reproduced by considering nearest and next-nearest neighbor interactions through hydrogen bonding. Because the hydrogen bond formed between donor (D) and acceptor (A) is cooperatively strengthened or weakened by a newly formed hydrogen bond at D or A, we have proposed the following notation for hydrogen-bonding patterns of monohydric alcohols: a(D)DAd(A)a(A), where a is the number of protons accepted by D (a(D)) or A (a(A)), and d(A) is the number of protons donated by A. The indicator of the hydrogen-bond strength, which is given by M(OH) = a(D) + d(A) - a(A), is correlated well with the nu(OH) wavenumber of the methanol molecule D participating in the a(D)DAd(A)a(A) pattern. The correlation between M(OH) and the hydrogen-bonding energy of the a(D)DAd(A)a(A) pattern has also been deduced from the calculation results for the clusters. The nu(OH) bands of methanol measured in the CCl4 solution and pure liquid have been successfully analyzed by the method proposed here.

Cryogenic neon matrix-isolation FTIR spectroscopy of evaporated ionic liquids: geometrical structure of cation-anion 1:1 pair in the gas phase.

Low-temperature infrared spectra of thermally evaporated ionic liquids, 1-ethyl- and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and bis(trifluoromethanesulfonyl)amide have been measured in a cryogenic Ne matrix. The experimental IR spectrum of bis(trifluoromethanesulfonyl)amide can be reproduced theoretically by not B3LYP/6-31G* but MP2/6-31G* calculation, which suggests that the vibrational analysis for ionic liquids composed of bis(trifluoromethanesulfonyl)imide anion would be more successfully performed using the MP2 calculation. By comparison of the matrix-isolation spectra of the ionic liquids with the MP2 calculation, their geometrical structures in the gas phase are determined to be of C(2-position)-H(+)...N(-) interaction structure, which corresponds to the geometry of the energetically second-lowest ion-pair structure. The present study may provide a valuable clue to understand a vaporization mechanism of ionic liquid.

Hydrodynamic Interpretation on the Rotational Diffusion of Peroxylamine Disulfonate Solute Dissolved in Room Temperature Ionic Liquids As Studied by Electron Paramagnetic Resonance Spectroscopy

Rotational motion of a nitroxide radical, peroxylamine disulfonate (PADS), dissolved in room temperature ionic liquids (RTILs) was studied by analyzing electron paramagnetic resonance spectra of PADS in various RTILs. We determined physical properties of PADS such as the hyperfine coupling constant (A), the temperature dependence of anisotropic rotational correlation times (τ(∥) and τ(⊥)), and rotational anisotropy (N). We observed that the A values remain unchanged for various RTILs, which indicates negligible interaction between the N-O PADS group and the cation of RTIL. Large N values suggest strong interaction of the negative sulfonyl parts of PADS with the cations of RTILs. Most of the τ(∥), τ(⊥), and (τ(∥)τ(⊥))(1/2) values are within the range calculated on the basis of a hydrodynamic theory with stick and slip boundary conditions. It was deduced that this theory could not adequately explain the measured results in some RTILs with smaller BF(4) and PF(6) anions.

Charge-Transfer Electronic Absorption Spectra of 1-Ethylpyridinium Cation and Halogen Anion Pairs in Dichloromethane and as Neat Ionic Liquids

The charge-transfer (CT) absorption bands of ion pairs composed of 1-ethylpyridinium (Epy(+)) and halogen anions (X(-): Cl, Br, or I) were measured in dichloromethane solutions of EpyX. The CT band of the Epy(+)I(-) ion pair shows clear splitting because of spin-orbit interaction in the excited state. The CT transition energy of an Epy(+)X(-) ion pair in a dichloromethane solution is related to electron affinity of X, which is in accordance with the Mulliken theory for CT bands. Extinction coefficients for the CT bands of the Epy(+)X(-) ion pairs in dichloromethane were determined using the measured absorbance, and the ion-pair concentration was estimated on the basis of electroconductivity. Structures of Epy(+)X(-) ion pairs were also evaluated on the basis of both quantum-chemical calculations and NMR spectroscopy. In addition, in the absorption spectrum measured for neat EpyI liquid, a broad band appeared at a longer wavelength side of the S1(ππ*) band. This new band has been assigned to the CT band of the Epy(+)I(-) ion pair formed in neat EpyI liquid.

Direct Spectroscopic Evidence of Photoisomerization in para-Methoxy Methylcinnamate Revealed by Low-Temperature Matrix-Isolation FTIR Spectroscopy.

The photoisomerization of para-methoxy methylcinnamate (p-MMC) has been studied by low-temperature matrix-isolation FTIR spectroscopy. In particular, the difference spectrum of the mid-IR frequency region (1100-1800 cm(-1)) allows us to distinguish the structural change before and after ultraviolet (UV) light irradiation at ≥300 nm and to convince that the cis-isomer is produced from the trans-isomer by comparing with the calculated IR spectra. Additionally, a reversible isomerization of p-MMC is demonstrated upon a sequential irradiation with different wavelengths of UV light. These findings provide a new insight into the electronic excited-state dynamics of p-MMC.

Pulsed EPR study on large dynamic electron polarisation created in the quenching of photo-excited xanthene dyes by nitroxide radicals in aqueous solutions

Dynamic electron polarisation (DEP) produced by the quenching of dye molecules in the triplet excited states by nitroxide radicals was investigated in aqueous solutions by pulsed electron paramagnetic resonance and transient absorption spectroscopy. An analysis of the measured quenching rate constants suggests that quenching is promoted by either exchange or charge-transfer mechanisms for a triplet dye and a doublet radical pair. An unusually large DEP on the radical was found generated in the nitroxide and Eosin Y or Rose Bengal systems in aqueous solutions. Quantitative analysis indicates that the DEP values in aqueous solutions range from −40 to −150 in the unit of thermal spin polarisation, which is in contrast to previously reported small DEP values of less than −10 for organic triplet molecules in benzene solutions [22–27,29,31,32]. From the theoretical analysis of DEP, an origin of this large DEP was attributed to the notably slow diffusion motion of Eosin Y and Rose Bengal in water.

Intensity Enhancement of Weak O2 a1Δg → X3Σg– Emission at 1270 nm by Collisions with Foreign Gases

Collision-induced near-IR emission of O(2) a(1)Δ(g) was investigated in O(2)/M (M = Ar, Kr, Xe, N(2), or CO(2)) gas mixtures, where the total pressure ranged from 10 to 100 atm, and gaseous O(2) dimol was excited with a pulsed dye laser at 630 nm through the simultaneous two-electron transition to prepare O(2) in the a(1)Δ(g) state. The a(1)Δ(g) → X(3)Σ(g)(-) emission intensity around 1270 nm increased with the number density of foreign gas (M) under constant O(2) number density. Emission enhancement efficiencies were in the order Xe > CO(2) > O(2) > Kr > N(2) > Ar; they are controlled by collisional enhancement during the near-IR emission at 1270 nm but not during photoabsorption at 630 nm. Efficiencies were converted into bimolecular rate constants to enhance the radiative a → X transition for the added gases. The rate constants were estimated as quadratically dependent on the molar refraction (or polarizability) of collision gas. The self-quenching rate constant was determined from the Stern-Volmer plot of the emission lifetimes measured in pure O(2).

Experimental and theoretical study of a new C10N8 compound. Reversible photoisomerization between 2,3,6,7-tetracyano-1,4,5,8-tetraazanapthalene and 4,5,9,10-tetracyano-1,3,6,8-tetraazacyclodeca-1,2,4,6,7,9-hexaene in low-temperature rare-gas matrices

Abstract Reversible photoisomerization of 2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene (TTN) in low-temperature rare-gas matrices was investigated by electronic absorption and Fourier transform infrared (FTIR) spectroscopies aided bydensity-functional-theory (DFT) calculations. The reactant, TTN, was found to change to 4,5,9,10-tetracyano-1,3,6,8-tetraazacyclodeca-1,2,4,6,7,9-hexaene (TTH) upon ultraviolet-light irradiation, while the product, TTH, returns to the original reactant, TTN, upon visible-light irradiation. The time-dependent DFT calculation led to the conclusion that the forward and backward photoisomerizations occur by way of the S 3 –S 0 transition of TTN and the S 1 –S 0 transition of TTH, respectively.