基态He2Ne^＋分子结构与性质的理论计算

利用Ｇａｕｓｓｉａｎ ９２程序和ＵＨＦ／６－３１Ｇ方法，计算了基诚Ｈｅ２Ｎ３＾＋分子的结构、能量，振动光主、热化学数据与静电参数。得到线型和弯曲的两处平衡结构。     

系列异金属类立方烷原子族化合物的振动光谱

通过振动光谱和Ｘ－射线结构分析数据的结合,归属了系列具有「Ｍ３ＹＳ３Ｍ′」（Ｍ＝Ｍｏ,Ｗ;Ｙ＝Ｏ,Ｓ;Ｍ′＝Ｃｕ,Ｓｎ,Ｓｂ,Ｐｂ,Ｂｉ）簇芯的异金属四核类立方烷原子簇化合物的主要振动谱峰。讨论了五种结构类型的光谱特征和成键状态,Ｍ′的加入使ｖＭ－（μ３－Ｙ）和ＶＭ－ｓ频率下降。当Ｍ′为过渡金属,例如Ｃｕ时,Ｃｊ与「Ｍ３ＹＳ３」结合紧密造成了Ｃｕ－Ｓ共价键相当的ｖＣｕ－ｓ振动频率,而当Ｍ′为主族金属时,ＶＭ′－ｓ远小于相应共价键的振动频率值。文中还对ｖＭ－Ｍ振动进行若干论述。     

双原子分子振动能级半量子化及量子理论的数值计算

利用半经典量子化理论和量子理论，分别采用Ｌｅｎｎａｒｄ－Ｊｏｎｅｓ势和Ｍｏｒｓｅ势，对双原子分子的振动能级给予了较为详细的数值计算。并将所得结果与部分实验数据进行比较，峄双原子分子的振动能级作了较为详细的 讨论。     

β-榄香烯振动光谱的量子化学从头计算

利用G98及GAMESS从头计算程序的RHF／6－31方法,对β－榄香烯的全部振动基频作了计算,并与实测红外光谱做了对比,归属了它们的振动模式,讨论了它们的特征基频,并对理论计算的振动频率进行了标度校正。     

XY2型分子伸缩振动与弯曲振动耦合研究

本文研究一种推广的局域模模型，我们用局域坐标描述非线性ＸＹ２分子的伸缩振动，用简正坐标描述弯曲振动；对用曲线内坐标写出的势能函数和Ｇ矩阵元进行Ｔａｙｌｏｒ展开，保留了弯曲振动与伸缩振动耦合的交叉项，获得各阶哈密顿量，略去了五次以上的高阶项；用它对实验数据进行非线性最小二乘法的拟合，得出各个势能参数值，并用它们计算了Ｈ２Ｏ分子的振动光谱，计算结果与实验数据符合得较好。     

显微红外光谱在摩擦学中的应用

用显微红外光谱测定了羟基植物油脂肪酸在摩擦过程中生成聚酯的特征吸收峰υc^as-o-c的波数，由聚酯的折合质量分析了特征吸收峰υc^as-o-c的波数位移，据此导出了羟基植物油脂肪酸的抗磨性顺序规律与振动吸收峰位置的内在联系，合理解释了υc^as-o-c从小到大的顺序（13，14－二羟基廿二酸＜13（14）－羟基廿二酸＝9，10－二羟基十八酸＜9，10，12－三羟基十八酯＜9（10）－羟基十八酸）与羟基酸的抗磨性从好到差的顺序（13，14－二羟基廿二酸＞13（14）－羟基廿二酸＝9，10－二羟基十八酸＞9，10，12－羟基十八酸＞9（10）－羟基十八酸）的一致性。13，14－二羟基廿二酸形成网状取酯膜，9（10）－羟基十八酸形成线状聚酯膜。     

钠原子微团簇Nan（n=2—5）的振动特性

采用距离相关的紧密结合模型，对Ｎａｎ（ｎ＝２－５）的振动特性进行了分析。通过求解Ｈｅｓｓｉａｎ矩阵和对距离相关的紧密结合分子动力学轨道所作的速度自关联函数的福里叶变换分析，得到了这些钠原子微团簇的振动频率。对Ｎａ２和Ｎａ３，这两种计算方法和实验，和从头计算法的计算结果一致，并对Ｎａ４和Ｎａ５的振动频率作了预言。     

CH3D分子3V2泛频态高分辨红外光谱的振动分析

用最小二乘法拟合ＣＨ３Ｄ分子６４２８ｃｍ＾－１附近振动带的１３８个能级，１０个振动常数。振动分析阐明带为ＣＨ３分子Ｃ－Ｄ对称伸缩振动３Ｖ２态，并与局域模振动理论计算值进行了比较。     

羟基碳酸钐中羟基位置及振动方式研究

稀土羟基碳酸盐是自然界稀土元素最基本的碳酸盐矿物形式, RE(CO_3)OH,是稀土碳酸盐类矿物和含水稀土碳酸盐矿物中的主要组成部分,在自然界有天然产出,同时碳酸盐矿物又是地球深部碳循环最重要的载体矿物,作为稀土元素主要的碳酸盐载体矿物,六方羟基碳酸钐稳定的结构能为稀土元素迁移提供稳定载体。目前对其结构中羟基氧配位连接方式及氢原子的准确占位情况的认识还存在许多争议,羟基碳酸盐类矿物研究还处在初级阶段,羟基对碳酸盐类矿物结构的影响的研究仍十分欠缺。采用六面砧大压机在高温高压(3 GPa, 800℃)下合成,粒度为10～20μm六方羟基碳酸钐单晶集合体。通过X射线单晶衍射分析得出,羟基碳酸钐为六方晶系,a=b=12.214 3(7)?,c=9.839 3(6)?,V=1 271.26(17)?~3,属P 6空间群。晶体结构模型显示在ab平面内,由Sm~(3+)和[OH]~-连接形成六方网,构成基本重复单层~2_∞[(OH)Sm_(3/3)]~(2+),碳酸根基团连接各层沿c轴延伸,中心Sm~(3+)呈9配位形式,与5个碳酸基团相连,其中4个单齿连接一个螯合连接;与3个羟基氧原子相连,确定配位多面体的具体形式。利用红外吸收光谱、拉曼光谱两种分析方法对初始样品结构进一步表征,尤其是对结构中的水进行了详细的解析。通过样品光谱学特征分析其内部基团振动模式与结构类型,特别是羟基在晶体结构中准确位置及振动特征。研究表明:六方羟基碳酸钐晶体中存在两种不同连接位态的羟基, 3 600～3 650 cm~(-1)谱带对应极化方向垂直(001)晶面,未能与层内氧原子形成氢键的羟基振动; 3 450～3 500 cm~(-1)谱带对应极化方向平行(001)晶面,可与层内氧原子形成氢键的羟基振动; 3 369～3 380 cm~(-1)谱带反应层间羟基的振动,更低频段3 230～3 250 cm~(-1)谱带则是O—H键长更短的羟基振动的体现。利用氘代样的红外吸收光谱验证H-D置换实验,由于D原子取代了H原子,导致ρ_(OH)摆动振动和ν_(OH)伸缩振动吸收峰消失,在2608.12cm~(-1)处出现O-D振动吸收峰,标志氘代完全,验证了氘代实验设计可行。作为可以改变岩浆地球动力学性质的羟基,常温常压下属性及矿物物理性质等对地球科学的基础研究有重要的参考价值。     

S2分子X^3—Σ^—g和B^3Σ^—u态的势能函数和振动光谱特征

应用实验光谱数据，导出了Ｓ２的基态分子Ｘ３Σ－ｇ和激发态Ｂ３Σ－ｕ的ＭｕｒｅｌＳｏｒｂｉｅ势能函数，并用ＱＣＩＳＤ（Ｔ）／６－３１１Ｇ方法对基态进行了计算，结果在吸引支出现了回避相交而产生了一个浅平极大，其他部位与实验结果符合甚好。计算了Ｂ３Σ－ｕ和Ｘ３Σ－ｇ态的全部振动能级，以及激发态（Ｂ３Σ－ｕ）振动能级≤９和基态（Ｘ３Σ－ｇ）振动能级≤３０之间的Ｄｅｓｌａｎｄｒｅｓ表。给出了Ｂ３Σ－ｕ－Ｘ３Σ－ｇ跃迁Ｃｏｎｄｏｎ抛物线，各振动态的计算结果与实验值很好符合。     

Analysis of the ir absorption profile of hydrargillite in the region of the valent vibrations of hydroxyl groups

An analysis of the complex absorption profile of hydrargillite in the region of stretching vibrations of the OH bond has been performed with the use of the method of direct fitting of the second-derivative curve. The observed profile is shown to contain an intense broad absorption band masked by eight mutually overlapping relatively narrow bands of structural OH groups of aluminum trihydroxide. The revealed broad absorption band is apparently due to the stretching vibrations of water molecules localized in the trihydroxide structure and the stretching vibrations of structural OH groups interacting with them via the hydrogen bond. An estimation of the basic spectral characteristics of the absorption bands forming the complex profile has been performed. Translated from Zhurnal Prikladnoi Spekroskopii, Vol. 67, No. 3, pp. 306–311, May–June, 2000.     

Temperature dependence of the Cs colloids absorption bands

Temperature dependence of the absorption bands due to Cs colloidal particles has been measured for colloids of different radii in additively colored CsBr and CsI. Large reversible shifts in the peak positions of the colloid bands are detected when we measure them at temperatures ranging between RT and LNT. The results are discussed and a tentative explanation based on the thermal change of Cs metal dielectric constants is proposed.     

Theoretical Study into the Dichroism of the Absorption Bands in the IR Spectra of Oriented Polymers

The IR dichroism of the polarized absorption bands of oriented polymers has been considered. An equation has been obtained that makes it possible to calculate the dichroism of the absorption bands for a different degree of the polymer orientation. This equation has been simplified especially for structurally insensitive absorption bands. In this case it allows one to determine the type of polarization of absorption bands.     

LSO-Ce fluorescence spectra and kinetics for UV,VUV and X-ray excitation

Abstract

LSO-Ce fluorescence emission and excitation spectra and decay kinetics have been measured for UV, VUV and X-ray excitation at RT and 80 K. The features of the fluorescence excitation spectra of two types of cerium centres in the region 3 to 6 eV are analysed in the assumption of competitative absorption between them. It is shown that the centres can have similar absorption bands. Forbidden energy bandgap for LSO is evaluated to be not less than 6.5 eV.     

Analysis of glucopyranoside trinitrate IR spectrum

The IR spectrum of 4-O-methyl-2,3,6-tri-O-nitromethyl-β-D-glucopyranoside has been interpreted in detail for the first time based on complete calculation of the normal vibration frequencies and absolute intensities of its IR absorption bands and a comparison of them with the corresponding experimental data. The results indicate that the location of the nitrates in cellulose nitrates can be determined experimentally from separate components of complicated absorption bands in the ranges 1700–1600 and 900–800 cm⁻¹ of the IR spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 43–51, January–February, 2008.     

羚羊角及其角塞的傅里叶红外光谱快速识别研究

采用傅里叶变换红外光谱(FTIR)技术,对羚羊角、羚羊角塞以及二者的混合物进行了对比研究。结果表明:羚羊角的红外光谱主要由蛋白质组分的特征吸收峰组成,而羚羊角塞的红外光谱主要由蛋白质和磷酸钙组分的特征吸收峰构成,二者的酰胺谱带、C—O伸缩振动谱带以及CH基团的伸缩振动谱带也均有明显区别。通过上述差异,可有效地鉴别羚羊角、角塞以及掺有角塞的羚羊角样品。该研究为羚羊角的掺伪和杂质检查提供了快速、科学的新方法,也为羚羊角的成分与质量评价体系研究提供了一定的信息。     

Study of the precipitation behavior of NaCl:Pb and KCl:Pb by optical spectroscopy2

The aggregation and precipitation behavior of lead in NaCl and KCl crystals has been systematically investigated by absorption and luminescence spectroscopy. For NaCl, absorption bands at 265 and 285 nm have been identified which correspond to intermediate stages in the formation of a double band (262–266 nm) associated with PbCl₂ precipitates. The kinetics of growth during ageing as well as the thermal annihilation behavior have been obtained for all bands. The emission spectra for excitation at those absorption bands have also been determined. For KCl, absorption bands at 265 and 280 nm develop during ageing at 160 and 200°C and their growth-rate is markedly enhanced by plastic straining. Their emission spectra involve a main band at $\text{\$}\text{?}$550 nm. In contrast to NaCl, no stage has been found where those absorption bands feed into a final band, which could be associated with PbCl₂ precipitates.     

化学混合物成分的太赫兹光谱分析

利用太赫兹时域光谱装置测量各种纯化合物的吸收谱,采用线性回归技术,对测量的化学混合物太赫兹吸收谱进行分析,得到样品中化合物的成分和相对含量.通过对蒽醌、苯醌和二苯甲酮混合物太赫兹吸收谱的研究,证实了利用整个测量波段的频谱作为化合物的指纹特征来分析化学混合物的成分和相对含量的方法是可行的.     

Forbidden character in electronic spectra of mono-halonaphthalenes

The singlet-singlet absorption and emission spectra of α-fluoro and the absorption spectra of α-chloro-, α-iodo-, and β-bromo-naphthalenes have been photographed and analyzed. The absorption spectra of all the four molecules show the presence of two discrete systems of bands, and the emission spectrum of α-fluoronaphthalene corresponds to the longer-wavelength system of absorption. With the α-chloro- and α-iodo-naphthalenes, the longer-wavelength system shows the appearance of pure electronic transition with weak bands, while the corresponding transitions in case of α-fluoro- and β-bromo-naphthalenes appear with the most intense bands of the system, as expected theoretically. The appearance of strong vibronic and weak electronic bands in the longer-wavelength system of the former two molecules has been interpreted as the interaction of totally symmetric vibrations, a rare example in the literature.     

含铅空位PbWO4晶体光学性质的模拟计算

为了研究钨酸铅晶体中铅空位对光学性质的影响,利用完全势缀加平面波局域密度泛函近似,按照能量最低原理采用共轭梯度方法,对含铅空位的PbWO4(PWO)晶体进行结构优化处理。计算了含铅空位的PWO晶体的电子结构、复数折射率、介电函数及吸收光谱,并与完整的PWO晶体进行了比较。结果表明：完整的PWO晶体在可见和近紫外区域内无吸收,而含铅空位的PWO晶体在可见和近紫外区域出现2个明显的吸收峰,这2个吸收峰可分解成4个高斯线型的吸收带,它们的峰值分别为350nm、405nm、550nm和670nm。可以得出这样的推论：PWO晶体中350nm、420nm、550nm和670nm吸收带的出现都与铅空位的存在有关。