红外光谱中溶剂效应机理初探——配位机制的提出

本文就红外光谱中溶剂效应机理提出了溶质和溶剂分子间的瞬时配位作用机制，认为同－溶质在不同溶剂中的振动波数不同，是由于这种瞬时配位作用改变了溶质价电子运动状态所致。据此提出了溶剂效砂的定量关系式，测定了七种溶剂配位效应常数。用这一套经验参数处理了几种取代苯甲酸的羰基伸缩振动的溶剂效应，得较好的线性关系。还发现羰基的振动波数与取代基的Ｈａｍｍｅｔｔ常数σ之间，羰基伸缩振动对溶剂效应的敏感度与σ之间，Ｈ     

Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

Evidence for the short-period oscillations in spin-resolved photoemission of thin Cr(110) films

The spin-resolved electronic structure of thin Cr overlayers on top of the Fe(110) surface was investigated by means of spin- and angle-resolved photoelectron spectroscopy. The initial fast drop of photoelectron spin-polarization at the Fermi level, followed by weak oscillatory behavior with the period of about 2 ML, can give an evidence for the first time spectroscopic observation of the short period oscillations in (110)-oriented thin Cr films.     

氯代5-氟脲嘧啶卟啉的红外光谱特性的研究

本文对新合成的对位及间位两类氯代苯基 5 氟脲嘧啶卟啉的红外光谱吸收峰进行了归属和总结 ,讨论了其红外吸收频率随取代基位置变化的规律。指出了苯环上的取代基为电负性强的基团时 ,由于场效应的存在 ,使被测化合物的羰基伸缩振动吸收峰的相对强度发生改变。同时 ,表明了嘧啶环上N原子发生了取代 ,形成单、双取代 5 氟脲嘧啶卟啉化合物的红外光谱特性。     

A numerical study of time-dependent schr?dinger equation for multiphoton vibrational interaction of NO molecule, modelled as Morse oscillator, with intense far-infrared femtosecond lasers

For the NO molecule, modelled as a Morse oscillator, time-dependent (TD) nuclear Schr?dinger equation has been numerically solved for the multiphoton vibrational dynamics of the molecule under a far-infrared laser of wavelength 10503 nm, and four different intensities,I = 1 × 10⁸, 1 × 10¹³, 5 × 10¹⁶, and 5 × 10¹⁸ W cm⁻² respectively. Starting from the vibrational ground state at zero time, various TD quantities such as the norm, dissociation probability, potential energy curve and dipole moment are examined. Rich high-harmonics generation (HHG) spectra and above-threshold dissociation (ATD) spectra, due to the multiphoton interaction of vibrational motions with the laser field, and consequent elevation to the vibrational continuum, have been obtained and analysed. Dedicated to Professor C N R Rao on his 70th birthday An erratum to this article is available at .     

Synthesis and structure of O-(arylcarbamoyl)butyrhydroximoyl chlorides

The O-(arylcarbamoyl)butyrhydroximoyl chlorides were synthesized, and the x-ray structural analysis (XSA) of one of them — O-(o-tolylcarbamoyl)butyrhydroximoyl chloride — was performed. It was established from the data of the XSA and the PMR spectra that all synthesized compounds are the Z isomers.Institute of Physiologically Active Substances, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 315–319, February, 1992.     

The hydrogen molecule in an arbitrarily oriented magnetic field

Summary The modifications induced by a magnetic field of arbitrary direction and intermediate strength (i.e not larger than 2.35·10⁵ tesla, the ?atomic tesla?) on the lowest singlet and triplet energy states of the hydrogen molecule are studied. Using a linear combination of products of field-modified atomic orbitals, it is found that increasing the field strength the depth of the singlet energy well increases and the equilibrium internuclear distance decreases, yielding more rigid and localized nuclear vibrations. For sufficiently strong fields perpendicular to the internuclear axis, the triplet state exhibits a bonding behaviour. An explanation of the above results is given in terms of the field-modified electronic-charge distributions in the internuclear region. Based on the thesis submitted by S. Basile to the University of Palermo for graduation in Physics.     

Electronic structure and vibrational spectra of cis-diammine(orotato)platinum(II), a potential cisplatin analogue: DFT and experimental study

Orotic acid (vitamin B₁₃) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C₅H₂N₂O₄)(NH₃)₂] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin.     

57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

塑料闪烁体的辐照特性

利用⁶⁰Co放射源分别对3种塑料闪烁体(BC-408, EJ-200, BC-404)进行辐照损伤研究, 比较辐照前后的透射谱、发射谱及光产额的变化, 发现3种闪烁体在低剂量具有较好的抗辐照性能; 当照射剂量超过1.44×10⁴Gy时,透射谱明显变坏, 光输出减少很严重, 但发射谱却保持不变.