高压下BaLiF3晶体光学性质的第一性原理研究

本文采用第一性原理方法, 在190 GPa的压力范围内, 计算了BaLiF3理想晶体和含空位点缺陷晶体的光学性质. 吸收谱数据表明, 压力因素不会导致BaLiF3晶体在可见光区有光吸收的行为. 空位点缺陷的存在会使得BaLiF3的吸收边红移(其中氟空位点缺陷引起的红移最显著) , 但这些红移不会导致它在可见光区内出现光吸收的现象. 波长在532 nm处的折射率数据显示, BaLiF3的折射率将随压力升高而增大. 氟空位点缺陷将导致BaLiF3的折射率增大, 但钡空位点缺陷和锂空位点缺陷的存在对其基本没有影响. 本文预测, BaLiF3晶体有成为冲击光学窗口材料的可能.     

高压下KMgF_3晶体光学性质的第一性原理研究

本文采用第一性原理的方法,在100 GPa的压力范围内,计算了KMgF_3的理想晶体和含空位缺陷晶体的光学性质.吸收谱数据表明,在100 GPa范围内,压力因素不会导致KMgF_3晶体在可见光区有光吸收行为.钾、镁和氟空位缺陷的存在会使得KMgF_3晶体的吸收边红移(其中氟空位缺陷引起的红移最显著),但这些红移不会导致它在可见光区出现光吸收的现象.能量损失谱数据显示,压力因素不仅会使得KMgF_3晶体的能量损失谱有蓝移的行为,而且还会引起它的较强谱峰个数发生变化.在100 GPa处的缺陷晶体数据指明,氟空位缺陷会导致其能量损失谱的两个较强谱峰的峰值强度明显降低.分析表明,KMgF_3晶体有成为冲击窗口材料的可能,并且本文所获得的结果对未来的实验探究有参考作用.     

高温高压下爆轰产物中不同种分子间的相互作用

给出了一种由特殊炸药的爆轰参数确定不同种分子间势函数参数的方法:由基于统计物理的爆轰产物物态方程程序类CHEQ,计算炸药RX-23-AB,HNB和PETN的爆轰参数,反推分子间的相互作用.给出了炸药主要爆轰产物H₂O,CO₂和N₂之间的非理想混合修正系数:K_N2-H2O=1.03,k_N2-CO2=1.035,k_H2O-CO2=0.96,将本文确定的不同种分子间势函数参数用于计算炸药PBX9404的超高压雨贡纽,获得了与实验一致的结果,验证了方法和参数的合理性.     

高温高压下爆轰产物分子间相互作用的研究

给出了一种由分子流体的冲击Hugoniot实验数据确定原分子之间和离解产物分子、原子相互间作用势参数的方法. 在较低压强下,采用Ross硬球微扰理论软球修正模型确定原分子之间的相互作用势参数;在较高压强下,采用基于统计物理的化学平衡方法来确定分子离解后的分子和原子之间的相互作用势参数. 与传统的由对应状态定律确定势函数参数的方法相比,所得到的势函数参数在很大的压强范围内都能较好地描述冲击实验. 关键词： 高温高压 化学平衡 冲击Hugoniot实验     

Studies of intermolecular interactions by matrix isolation vibrational spectroscopy: Self-association of water

The mid- and far-infrared spectra of water in argon and nitrogen matrices have been reinvestigated. The water molecule rotates in an argon matrix, but in a nitrogen matrix two low-frequency bands are attributed to libration of the water monomer about its A and C rotational axes. Combinations of these modes with the stretching and bending modes of the water monomer were observed. A detailed concentration-dependence study enabled bands to be attributed to dimer, trimer, and tetramer or higher multimers. The dimer and trimer were both found to have open chain structures, whereas tetramer or higher multimer species appear to be predominantly cyclic. Intermolecular modes, observed for dimer and trimer in the far-infrared spectra, are tentatively assigned.     

X-ray absorption spectroscopy and high pressure

Abstract

The difficulties of the adaptation of high pressure to x-ray absorption are presented. The advantages of the energy-dispersive geometry are discussed as well as the future improvements expected with the new synchrotron radiation sources.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

The influence of the nature of a substituent on the parameters of the intra- and intermolecular interactions in molecules of cross-conjugated ketones

We have quantitatively analyzed the vibronic parameters of two cross-conjugated δ-dimethylaminoketones. The presence of the –N(CH₃)₂, C=O, and –NO₂ groups in the benzene ring has been shown to affect the manifestation of the vibronic parameters of characteristic bands that describe the state (vibrations, types of deformation upon excitation) of polyene systems with aromatic rings. Data on the influence of the nature of the substituent on the parameters of intra- and intermolecular interactions in the examined compounds have been presented.     

Single-crystal elasticity of the rhodochrosite at high pressure by Brillouin scattering spectroscopy

ABSTRACT

The sound velocity properties of single-crystal rhodochrosite (MnCO₃) were determined up to 9.7?GPa at ambient temperature by Brillouin scattering spectroscopy. Six elastic constants were calculated by a genetic algorithm method using the Christoffel's equations at each pressure. The elastic constants increased linearly as a function of pressure and its pressure derivatives ?Cij/?P for C₁₁, C₃₃, C₄₄, C₁₂, C₁₃, C₁₄ were 5.86 (±0.36), 3.82 (±0.44), 2.06 (±0.39), 5.07 (±0.27), 5.34 (±0.44), 1.52 (±0.24), respectively. Based on the derived elastic constants of rhodochrosite, the aggregate adiabatic bulk and shear moduli (K_s and G) were calculated using the Voigt-Reuss-Hill averages and the linear fitting coefficients (?K_s/?P)_T and (?G/?P)_T were 5.05(±0.26) and 0.73(±0.05), respectively. The aggregate V_p of rhodochrosite increased clearly as a function of pressure and its pressure derivative ?V_p/?P was 7.99(±0.53)?×?10^?2?km/(s?GPa), while the aggregate V_s increased slowly and ?V_s/?P was only 1.19(±0.12)?×?10^?2?km/(s?GPa). The anisotropy factor for As of rhodochrosite increased from ～40% at 0.8?GPa to ～48% at 9.7?GPa, while A_p decreased from ～19% to ～16% at the corresponding pressure.     

Studies of intermolecular interactions by matrix isolation vibrational spectroscopy and normal coordinate analysis: Self-association of hydrogen cyanide

A detailed study of the infrared spectra of hydrogen and deuterium cyanide in noble gas, nitrogen and carbon monoxide matrices at 4 K and 20 K has enabled the bands observed to be assigned to monomer, dimer, trimer, tetramer and higher multimer species. Force constants calculated for the linear dimer are used to predict the spectrum of the trimer. The nature of the trapping sites occupied by the monomer and linear dimer, and the structure and trapping site of a second type of dimer observed only in argon matrices, are discussed.     

Investigation of intra- and intermolecular transfer processes by picosecond fluorescence gating

Fluorescence up-conversion is a promising technique for the investigation of ultrafast processes within and between poly-atomic molecules. Conditions are discussed for up converting broad-band fluorescence efficiently with a time resolution better than 1 ps. Experimental results are presented on vibrational relaxation in the first excited singlet state, internal conversion, and intermolecular energy transfer in liquid solutions.     

X-Ray absorption spectroscopy investigations of the hydrophobic hydration of krypton at high pressure

The development of third-generation synchrotron radiation sources has created considerable opportunities for the investigation of systems under extreme sample conditions of pressure and temperature. This paper presents the application of a recently developed pressure cell and pressurization and circulation system to the investigation of the hydrophobic hydration of noble gases by X-ray absorption spectroscopy. This system operates in the pressure range from 1 bar to 1 kbar, and allows for mixing of gaseous and liquid components and the control of the ultimate gas in liquid concentration. First results demonstrate the remarkable resilience of the first hydration shell of a nonpolar solute (krypton) to the application of pressure in the 150 bar to 700 bar range. These results suggest questioning the conclusions of some recent computer simulations, in particular with regards to the potential impact of such studies on our understanding of pressure induced protein denaturation.     

Optical microscopic,X-ray diffraction,and electrical resistance studies of CuCl at high pressure

Electrical resistance and X-ray diffraction measurements and also optical observations under a polarizing microscope were made on CuCl to pressures in excess of 12.5 GPa at room temperature using a diamond anvil cell. Resistance measurements were also performed in a piston-cylinder apparatus to pressures of approximately 5.5 GPa at room temperature. Three samples of CuCl prepared by different methods were examined. No anomalous pressure dependence in electrical resistance was found in the pressure range studied, and no dramatic changes in optical transmission were observed up to pressures of approximately 10.0 GPa. Optical observations and X-ray diffraction measurements indicate the existence of four phases in the pressure range studied, including a nonconducting black opaque phase which grows with time when CuCl is left for several days at the highest pressures.     

高压下LiYF4晶体光学性质的第一性原理研究

本文采用第一性原理方法,在100 GPa的压力范围内, 计算了LiYF4理想晶体和含空位点缺陷晶体的光学性质.吸收谱数据表明,在100 GPa范围内,压力和相变因素的存在不会改变LiYF4晶体在250-1000 nm的波段内没有光吸收的事实. 氟、钇空位点缺陷的出现会使得LiYF4的吸收边蓝移,而锂空位点缺陷将导致它的吸收边微弱红移(但在250-1000 nm的波段内它仍不具有光吸收行为).波长在532 nm处的折射率数据显示, 在LiYF4的三个结构相区,其折射率均随压力的增加而增大. LiYF4从白钨矿结构到褐钇铌矿结构的相变会使得其折射率略微增加,但从褐钇铌矿结构到类黑钨矿结构的相变将导致其折射率显著降低. 同时,空位缺陷的存在将引起LiYF4的折射率明显增大. 分析指明,LiYF4有成为冲击窗口材料的可能. 本文所获得的信息对未来的实验研究有参考作用.     

Phase Transition and vibration properties of MnCO3 at high pressure and high-temperature by Raman spectroscopy

The high pressure and high-temperature behavior of MnCO₃ was investigated up to 55?GPa at ambient temperature and up to 573?K at ambient pressure by Raman spectroscopy, respectively. Some new modes were detected at ～16 and ～32?GPa, which were assigned to MnCO₃-I below 16?GPa and to MnCO₃-II above 32?GPa, and to a coexisting phase of them in between. The high pressure vibration properties of all Raman modes, especially high frequency modes, were systematically reported. The coexisting phase of MnCO₃-I and MnCO₃-II had much easier compressibility than the MnCO₃-II phase. The thermal stability of MnCO₃ was at least to 573?K and its thermal expansion along the c axis was easier than a and b axes.     

Probing structural stability of double-walled carbon nanotubes at high non-hydrostatic pressure by Raman spectroscopy

Theoretical calculations predict that the collapse pressure for double-walled carbon nanotubes (DWCNTs) is proportional to 1/R ³, where R is the effective or average radius of a DWCNT. In order to address the problem of CNT stability at high pressure and stress, we performed a resonance Raman study of DWCNTs dispersed in sodium cholate using 532 and 633 nm laser excitation. Raman spectra of the recovered samples show minor versus irreversible changes with increasing I _D/I _G ratio after exposure to high non-hydrostatic pressure of 23 and 35 GPa, respectively. The system exhibits nearly 70% pressure hysteresis in radial breathing vibrational mode signals recovery on pressure release which is twice that predicted by theory.     

Raman spectroscopy of topiramate under high pressure conditions

Topiramate is a white crystalline solid with powerful anticonvulsant activity and is used to treat epilepsy. Drug manufacturing involves various physical and chemical processes, which may lead to the formation of an unexpected, or undesired, crystalline phase, in a phenomenon known as polymorphism. In this paper, the behavior of topiramate crystal is studied under pressures up to 10.8 GPa using Raman spectroscopy. Under the conditions employed, Raman spectra from topiramate under pressure showed no strong evidence of a phase change, although amorphization may be considered. This may be accounted for by its crystal structure, comprising oppositely running chains of topiramate molecules linked by asymmetric hydrogen bonds, which pose a kinetic barrier against a structural change. It is not yet safe to rule out the existence of topiramate polymorphs, which could possibly be obtained under special crystallization conditions, but not after compression, at least up to 10 GPa. Copyright © 2009 John Wiley & Sons, Ltd.     

Elasticity of hexagonal-closed-packed cobalt at high pressure and temperature: a quasiharmonic case

We performed high-resolution inelastic x-ray scattering measurements on a single crystal of hcp cobalt at simultaneous high pressure and high temperature, obtaining 4 of the 5 independent elements of the elastic tensor. Our experiments indicate that the elasticity of hcp-Co is well described within the quasiharmonic approximation and that anharmonic high-temperature effects on the elastic moduli, sound velocities, and elastic anisotropy are minimal at constant density. These results support the validity of Birch's law and represent an important benchmark for ab initio thermal lattice dynamics and molecular-dynamics simulations.