Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

Copper—A “Modern” Bioelement

Copper is a bioessential element in biology with truly unique chemical characteristics in its two relevant oxidation states +I and +II. Significant progress has been made in recent years in the elucidation of the frequently surprising biochemistry of this trace element. Those advances were especially furthered through mutual stimulation involving results from biochemistry, molecular biology, and medicine on one hand and the synthesis as well as the structural and spectroscopic characterization of low molecular weight model complexes on the other. The most notable features of protein-bound active copper are its almost exclusive function in the metabolism of O₂ or N/O compounds (NO, N₂O) and its frequent association with oxidizing organic and inorganic radicals such as tyrosyl, semiquinones, superoxide, or nitrosyl. This unique biological role of copper can be rationalized given its chemical and assumed evolutionary background.     

Assessing the non-specific hydroxyl radical scavenging properties of melanoidins in a Fenton-type reaction system

Soluble high molecular weight fraction (>10 kDa, named melanoidins) was isolated from Maillard reaction model systems, coffee, beer and sweet wine by ultrafiltration. Deoxyribose method was adjusted for measuring the hydroxyl radical scavenging properties of melanoidins. The presence of competitive melanoidins with deoxyribose for OH decrease the rate of deoxyribose degradation. Possible interferences to the deoxyribose method have been evaluated. Most of isolated melanoidins exhibited a variable and measurable non-site-specific hydroxyl scavenging activity in a Fenton-type reaction system. The iron reducing properties of melanoidins at the reaction conditions were evaluated with ferrozine. It has established a kinetic approach to assess the second rate constants of hydroxyl radical scavenging reactions of melanoidins. This approach may be a valuable tool for addressing the structure-activity relationships of melanoidins in a future. There is no correlation between browning (absorbance at 420 nm) and efficiency for scavenging hydroxyl radicals in solution.     

甲醇分子(CH3OH)光谱性质的理论计算

研究了气相甲醇分子(CH3OH)基态和激发态性质。在对不同方法基组所得计算结果和实验结果进行比较之后,选用MP2(full)/6-311++G(2d,2p)理论方法进行计算,得到甲醇分子(CH3OH)基态和三重激发态的几何结构、能量以及频率信息;频率计算显示基态和三重态都为稳定构型。从三重态的结构出发,解释了三重态势能面为排斥型势能面的合理性。计算了甲醇分子单重激发态的垂直激发能,比较不同方法不同基组计算的甲醇分子单重激发态的垂直激发能,发现用TDDFT 中的b3p86方法使用6-311++G**基组的计算值和实验值符合得最好。计算得到的甲醇分子在MP2(full)/6-311++G(2d,2p)的绝热电离能和垂直电离能分别为11.18eV和11.32eV;计算得到的绝热电子亲和势与垂直电子亲和势分别为0.888eV和0.893eV。计算结果对实验研究有指导意义。     

Acoustooptic extension of the frequency tunability of CW CO2 lasers: New FIR lasers emissions from CH3OH and13CH3OH

We have increased the frequency tunability of our CW waveguide CO₂ lasers by means of an acoustooptic amplitude modulator, operating at the fixed frequency of 90 MHz. The up-shifted, or down-shifted, laser optical sideband can be generated independently by adjusting the orientation of the modulator. The efficiency is larger than 50%. The frequency tunability of the CO₂ laser around each laser line is thus increased by 180 MHz. To demonstrate the possibilities of this method, a source composed of the above modulator and of a CW, 300 MHz tunable waveguide CO₂ laser has been used for the search of new large offset FIR laser lines from optically pumped CH₃OH and¹³CH₃OH molecules. As a result 15 and 10 new large offset laser lines were discovered respectively. New assignments of some laser lines are also proposed. We have also measured the Stark effect, the offset, and the polarization of other already known lines. In particular a Stark effect frequency tuning of about 1 GHz is demonstrated for a laser line at 208.399 m.     

A twin optically-pumped far-infrared CH3OH laser for plasma diagnostics

A twin optically-pumped far-infrared CH₃OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH₃OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO₂ laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan.     

Structures and stabilities of the donor–acceptor complexes HXPY (X=Al,B; Y=H,F, OH)

The optimized geometries, complexation energies, etc. of HXPY (X?=?Al, B; Y?=?H, F, OH) donor–acceptor complexes have been investigated at the B3LYP/6-311+G(d,p), MP2/6-311+G(d,p) and/or CCSD(T)/6-311+G(d,p) levels. The results show that HBPY (Y?=?H, F, OH) is more stable than the corresponding HAlPY (Y?=?H, F, OH), F (or OH) substitution on phosphorus results in decreasing complex stability, and the stronger the electron-attracting nature of the substitution atom, the more stable the complex. Moreover, the thermodynamic and kinetic properties of the formation reaction of these donor–acceptor complexes were also examined within the temperature range 200–800?K using the general statistical thermodynamics and Eyring transition state theory with Wigner correction. It is concluded that the formation of HBPY is thermodynamically favoured over that of the corresponding HAlPY, especially at low temperature, and is kinetically favoured over that of the relevant HAlPY (Y?=?H, F, OH), especially at high temperature.     

The resonant secondary emission of the F center in alkali halides

The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states.     

用浓度调制光谱法测量水汽辉光放电中OH和H2O的布居数变化

本文使用波长为2.8 μm的分布式反馈激光器来测量水汽辉光放电产生的物种. 使用浓度调制光谱仅观察到OH自由基和瞬态H₂O分子的吸收光谱. 吸收峰的强度和方向随解调相位而变化,但是H₂O的一个吸收峰的方向始终与其它峰相反. OH和H₂O的不同光谱取向反映了能级中粒子数量的增加或减少. 如果在放电过程中可以检测到更多的瞬态物种,则可以更好地研究H₂O的激发、电离和分解动力学. 研究表明,浓度调制光谱的解调相位关系可以用来研究分子能级的布居数变化.     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.