Evaluation of nonisothermal band models for H2O

Comparisons of predicted and measured radiance spectra for nonuniform hot H₂O gas samples are reported. The predicted spectra are generated with band models formulated in a companion paper, and band model parameters constructed to handle optical path temperature variations from 200 to 3000°K. The model identified in the companion paper as the intuitive derivative approximation is shown to be superior to the traditional Curtis-Godson approximation in treating general optical paths along which high degrees of nonuniformity occur.     

H2O and D2O spin-isomers as a mediator of the electron transfer in the reaction center of purple bacteria

The dynamics of charge separation states has been numerically simulated in order to calculate the polarization (in the third order of the perturbation theory) and its evolution in a pulsed optical field. Time evolution of the rotational states of the ortho-D₂O isomer with a nonzero magnetic momentum and mixed ortho/para-D₂O states have been calculated on the basis of the Liouville equation for the density matrix and the Redfield relaxation model for molecular aggregates. Frequencies similar to the known experimental frequencies of the modulation of the kinetics (electron transfer) of the reaction centers special pair in purple bacteria are selected from the set of calculated rotational-resonance frequencies. This semiquantitative coincidence of frequencies (within the experimental error) confirms the previously stated hypothesis, according to which the ortho-H₂O (D₂O) spin isomer can play a role of mediator during electron transfer in the reaction centers of purple bacteria.     

烟草中CuZnSODⅢ的荧光光谱及pH值和H2O2敏感性

考察了烟草中CuZnSODⅢ在不同pH值和H2O2加入量前后的荧光光谱。用同步荧光技术区分蛋白质分子中酪氨酸和色氨酸残基的荧光,进一步结合荧光猝灭现象和三维荧光特征,探讨发色团微环境及蛋白质分子构象行为,推断得出H2O2对荧光的猝灭属于氧化还原猝灭和双分子碰撞猝灭双重机制,及色氨酸残基对pH值和H2O2更为敏感的结论。     

Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

利用波长调制光谱技术测量高温环境中的气体压强、温度和H_2O组分浓度

利用基于可调谐半导体激光器的扫描波长调制光谱技术,实现了高温燃烧场内气体参数的测量。提出了基于迭代算法实现气体压强、温度和组分浓度同时测量的方法,迭代算法具有收敛速度快以及对初始值不敏感等优点。采用频分复用技术,利用两条H_2O吸收谱线(7 454.45和6 806.03cm-1)的谐波信号,对高温燃烧场进行了实验研究,并将气体压强、温度和H_2O组分浓度测量结果与压力传感器、热电偶和直接吸收光谱法的测量结果进行比较,结果表明,基于波长调制光谱技术测得的气体压强、温度和H_2O浓度与预测值基本符合,最大偏差分别在7.6%,8.1%和7.5%以内。此方法具有多参数同时测量、免标定等显著优势,但由于依赖的参数较多,容易对测量精度造成影响。     

H2O/N2脉冲流光放电和介质阻挡放电发射光谱比较

本文采用脉冲流光放电和介质阻挡放电两种放电形式分别获得了H2O / N2等离子体的发射光谱。 OH荧光辐射在两种放电等离子体中均出现,而Ha荧光辐射仅存在于脉冲流光放电等离子体中。实验还对脉冲流光放电条件下H、OH 荧光信号进行了时间分辨测量,结果显示Ha荧光信号滞后OH荧光信号约10 ns。根据时间分辨测量结果以及水分子离解的相关文献,实验判断等离子体内水分子离解的主要产物是基电子态的H原子和OH自由基,Ha荧光辐射源于快电子对H原子的次级碰撞激发。介质阻挡放电等离子体的放电脉冲宽度较窄,不能对基态 原子进行有效地次级碰撞激发,所以H2O / N2介质阻挡放电等离子体发射光谱中没有出现Ha荧光辐射。实验结论证实放电脉冲宽度对放电等离子体内次级碰撞激发过程有影响。     

FT-IR Study of the Interaction Between H2O,D2O,HOD, and Pyridines

Abstract

The complexes between H₂O, D₂O, HOD and pyridine have been studied in 1,2-dichloroethane by FT-IR spectrometry. Equal splittings of the stretching bands of H₂O and D₂O about their uncoupled vibrations are observed. The coupling between the asymmetric and symmetric vibrations reaches a value of zero when the band separation is greater than 500 cm^?1 for the OH vibrations and 365 cm^?1 for the OD vibrations. The v_OH stretching frequencies of the HOD ‥ complexes and the v_OD stretching frequencies of the DOH‥ complexes increase by complex formation. These features are explained by an electronic reorganization within the hydrogen bond.     

Near-i.r. Absorption of H2O and D2O in the liquid and supercooled range

Summary Results are reported on near-i.r. absorption spectra of H₂O and D₂O down to the temperature region of supercooled liquid. No anomalous behaviour is observed when the absorbance at any given frequency is studied as a function of temperature. A critical-exponent behaviour strikingly correlating with that exhibited by transport properties is instead observed when spectral deconvolution methods are used. Results are discussed in relation with current views on water structure, based on molecular-dynamics simulation results and connectivity calculations.

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Riassunto Si riportano risultati sugli spettri di assorbimento i.r. di H₂O e D₂O fino alla regione di temperature del liquido sopraraffreddato. L'andamento dell'assorbanza a frequenza costante in funzione della temperatura non mostra alcuna indicazione di comportamento anomalo. Al contrario, quando gli spettri sono analizzati con metodo di deconvoluzione, si osserva un comportamento di tipo esponente critico, che correla straordinariamente bene con quello mostrato dalle proprietà di trasporto. I risultati sono discussi anche in relazione ai piú recenti modelli di struttura dell'acqua, derivanti dai risultati di simulazione e dai calcoli di connettività.

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Резюме Приводятся результаты для спектров инфракрасного поглощения H₂O и D₂O для температур переохлажденной жидкости. Не обнаружено аномального поведения, когда поглощательная способность при заданной частоте изучается как функция темпетатуры. Напротив, при анализе спектров с помощью спектральных методов конволюции наблюдается поведение типа критической экспоненты, которое коррелирует с поведением, определяемым транспортыми свойствами. Полученные результаты обсуждаются в связи с недавними моделями структуры воды, полученными на основе моделирования молекулярной динамики и нычислений связности.

     

Measurement of diffusion coefficients of thallium ion in H2O and D2O systems at different concentrations

Sliding cell method, developed in our laboratory, has been used to measure the inter diffusion coefficient of thallium ion in thallous sulphate solution over a wide concentration range using both water and heavy water as solvent at 35°C. The results have been analysed from the point of view of both ion-ion and ion-solvent interactions. The comparison of the diffusivities of the same ion in D₂O and H₂O electrolyte solutions at the same temperature indicate that the addition of salt affects the two solvents differently.     

A difference in the electromagnetic properties of D2O and H2O ice revealed by resonance measurements

The dielectric parameters of H₂O and D₂O ice samples were studied by a resonance technique in the region of 6 GHz. The ratio of the resonance curve halfwidths at half maximum was measured for light and heavy ice in the temperature range from 0 to ?130°C. The temperature dependences of the resonance peak asymmetry of the two types of ice are qualitatively different. The ratio of the higher-frequency halfwidths at half maximum to the lower-frequency one plotted versus temperature exhibits a positive slope for light ice and a negative slope for heavy ice. It is suggested that the difference reflects the different quantum statistics of the hydrogen and deuterium nuclei in ice.     

MOCVD法生长ZnO薄膜时氧源 t-BuOH和H2O的比较研究

以活性较低的叔丁醇(t-BuOH)和水(H₂O)作为氧源,采用MOCVD技术生长了ZnO薄膜。研究发现,t-BuOH作为氧源可以有效地抑制其与锌源之间的气相预反应,比H₂O作为氧源进行ZnO薄膜的外延生长具有更高的生长速率,得到的ZnO薄膜晶体质量更优,同时载流子的迁移率可以达到37.0 cm²·V^-1·s^-1, 表明t-BuOH更适合作为氧源通过MOCVD系统生长ZnO薄膜。     

Helium diffusion through H2O and D2O amorphous ice: observation of a lattice inverse isotope effect

The diffusion of He through both H2O and D2O amorphous solid water (ASW) has been measured between 55 and 110 K. We find the diffusion rate is dependent on the isotopic composition of the ASW lattice. This lattice isotope effect is the "inverse" of a normal isotope effect in that diffusion is faster in the heavier (D2O) isotope. Transition state theory calculations show that the inverse isotope effect is due to a tight transition state and predominantly arises from the zero-point vibrational energy associated with the frustrated rotational modes of water in the lattice.     

On the additivity of atomic and molecular dipole properties and dispersion energies using H,N, O,H2, N2, O2, NO,N2O,NH3 and H2O as models

The zeroth-order theory of intermolecular forces is used to derive additivity relations for rotationally averaged molecular dipole properties and dispersion energy constants by assuming that a molecule is comprised of non-interacting atoms or molecules. Some of the additivity rules are new and others, for example the mixture rule for dipole oscillator strength distributions (DOSDs), Bragg's rule for stopping cross sections and Landolt's rule for molecular refractivities, are well known. The additivity rules are tested by using previously constructed DOSDs and reliable values for the dipole oscillator strength sums S_k , L_k and I_k , and dispersion energy constants C ₆, for H, N, O, H₂, N₂, O₂, NO, N₂O, NH₃ and H₂O as models. It is found that additivity is generally unreliable for estimating molecular properties corresponding to k < -2. Generally for k ≥ -2 and for C ₆, and if the hydrogen molecule is used to represent the hydrogen atom in the additivity rules, the additivity relations yield results that are reliable to within ?20 per cent and the estimates improve substantially as k increases. The effects of molecule formation on DOSDs is examined by comparing the various molecular DOSDs with the sum of the DOSDs for the atoms making up the molecules. Molecule formation results in a net decrease in the amount of dipole oscillator strength for low excitation energies and a compensating net increase for higher energies in a region extending from the absorption threshold to about 100 eV. This is shown to imply that estimates of the stopping average energy I ₀, obtained by using bona fide atomic I ₀ values, are lower bounds to the correct molecular I ₀ results.     

星际H2O与OH分子脉泽的统计与激发机制探讨

报告了大质量恒星形成区的星际分子脉泽巡天观测结果.所观测到的H2O与OH分子脉泽可分为三类,它们的数量近似相等,寿命亦近似相等～105年,但HⅡ区普遍短缺.提出了一种新的辐射机制模型,它克服了旧辐射模型的缺点,可以解释星际H2O与OH脉泽的成因,以及作者的观测统计结果.