用Reichardt''''s Dye研究碳酸酯溶剂极性的经验参数ET(30)

使用2,6-二苯基-4-(2,4,6-三苯基-1-吡啶鎓)苯氧内盐染料(Reichardt's Dye)研究锂离子电池中非水电解质溶剂碳酸酯的极性,并测量极性经验参数ET(30)碳酸乙烯酯为48.6,碳酸丙烯酯为46.1,2,3-碳酸丁烯酯为45.7,碳酸二甲酯为39.0,碳酸甲乙酯为37.3,碳酸二乙酯为37.0.LiClO4加入到碳酸酯溶剂中,显色剂受到离子的盐效应影响,表现为溶液体系的ET(30)值增加,极性增大.由于溶液中粒子间的相互作用不同,环碳酸酯与链状碳酸酯极性变化趋势不同.极性大的溶剂易形成Ar-O-…solvent…Li+结构,起到缓冲作用,抑制了显色剂的酚氧基与Li+直接作用.     

含芯电子相关能修正的G2理论——G2(ful)

A general method in considering the core electronic correlation energies has been proposed and introduced into the standard Gaussian-2 (G2)[7] theory by small post-Hartree-Fock calculations. In this paper an additional MP2(FC)/6-31G(d) calculation over the G2 procedures is employed and examined in modification in modification to the flaw of Frozen-Core (FC) approximation of G2 vai eq.:
ΔE(full)= E[MP2(full)/6-31G(d)]-E[MP2(FC)/6-31G(d)]
where the MP2(full)/6-31G(d) energy has been obtained in the molecular geometry optimizations. This energy, ΔE(full), is directly added into the total G2 energy of a molecule in facilitating the effect of core electronic correlations for each molecule in chemical reactions. It has been shown that the over-all average absolute deviation for the 125 reaction energies of the G2 test set (test set 1) is slightly reduced from 5.09 to 5.01 kJ, mol(-1) while for the 55 D0 values, which have been used for the derivation of the A coefficient of the empirical High-Level...更多-Correction (HLC), it is also reduced from 4.99 [for both G2 and G2(COMPLETE)[8]]to 4.77 kJ• mol(-1). In addition, larger errors (greater than ±8.4 kJ•mol(-1) for the D0 energies are improved, especially for the largest error of the D0 of SO2 This error is reduced from 21.3 to 15.4 kJ. mol(-1), in which the experimental geometry would further reduce it by 7.1kJ.mol(-1)[8]. Another improvement is the absolute value of the A coefficient in HLC being reduced from 4.81 for G2 to 4.34 milli-hartrees which is believed to be useful in isolating the relationship between the HLC and the FC approximation. Modifications to the original G2 from this work is denoted as G2(fu 1) and thus the G2 (fu 1) total energy for a molecule is
E[G2(fu 1)]= E[G2]+Δ E(full)h
with a new ΔE[HLC] =-0.19α- 4.34nβ milli-hartree.     

某些离解能、电子亲合能等的G2计算与评价

PoPle及其合作者创立的Gaussian再简称GZ）理论［‘－’］，以其相对可靠的化学精度和相应较小的计算量已经引起了实验和理论化学家们的广泛关注问．p。ple等人在他们的GZ文章中强调了GZ的理论计算结果在研究离解能等化学问题中与精确实验数据之间的偏差普遍不大于全8．狄J规厂‘．我们近期的研究表明＊’1，＊2和优（＊则在计算一般化学反应能量中，绝大多数情况下，分别都能保证结果与实验偏差在全8．4和士13kJ·mol‘以内．近年来，已有大量的研究工作表明，GZ的理论结果已广泛用于未知实验数据的预测、已有实验数据的评价和修正等…     

选相示波伏安法

选相示波伏安法毕树平，都思丹，高鸿（南京大学化学系，２１０００８）关键词示波计时电位法，选相示波伏安法，切口示波计时电位法是利用ｄＥ／ｄｔ～Ｅ曲线上切口的高度或深度进行定量分析的方法［１］，但由于ｄＥ／ｄｔ曲线主要反映充电电流的变化，从而使该方法的检...     

Vibrational Spectroscopic Study on Ion Solvation and Association of Lithium Perchlorate in 4-Methoxymethyl-ethylene Carbonate

Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate. The splitting of ring deformation band and ring ether asymmetric stretching band, and the change of carbonyl stretching band suggest that there should be a strong interaction between Li^＋ and the solvent molecules, and the site of solvation should be the oxygen atom of carbonyl group. The apparent solvation number of Li^＋ was calculated by using band fitting technique. The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions. On the other hand, the band fitting for the ClO4^- band revealed the presence of contact ion pair, and free ClO4^- anion in the concentrated solutions.     

机·能·美——专访SONY设计中心设计经理市川和南及明星设计师小笠原伸一

卓越，源于品质可靠的产品体系。每一款高品质产品的问世，背后总是凝聚着更多的幕后英雄。SONY PSP、SONY VAIO UX、SONY VAIO TX……这些耳熟能详的名字都是出自SONY幕后的优秀设计师之手。SONY的产品设计世界闻名．而这些默默无闻的英雄又是如何构思．如何设计的？我们这次有幸揭开了他们的庐山真面目。     

超表面透镜的像差分析和成像技术研究

传统光学透镜及光学系统基于光传播效应实现电磁波调控功能,其体积较大、不易集成.而超表面是由人工亚波长尺度单元构成的二维平面结构,由于其相对于传统透镜具有超薄的优势,并且可以实现对光场的任意调控,近年来在光学成像领域得到广泛研究和应用.本文阐述了超表面透镜的工作原理,分析了超表面成像透镜的单色像差和色像差成因以及对应的像...     

基于小程序的大学校园闲置书籍交易平台设计与开发

目前大多数高校针对闲置书籍的收集与贩卖,大多局限于闲置群与线下面对面交易,交易方式存在不规范性、危险性等诸多问题。文章就如何解决以上问题进行深入探讨,主要采用了线上线下(Online to Offline, O2O)的双重模式,并且立足于高校,采用借力思想,充分利用高校的人力、信息等资源。文章通过制作微信小程序,力求实现高校闲置书籍的规范化售卖,促进其高效利用,营造一个为师生提供集文化交流和丰富信息为一体的高品质服务的闲置书籍交易平台,对于二手交易类的小程序开发与设计具有一定的参考借鉴价值。     

GaAs基通孔刻蚀的崩边形成机理研究

在砷化镓(GaAs)集成无源器件(Integrated Passive Device, IPD)的制作工艺中,通孔刻蚀是一道重要环节。蚀刻孔边缘的GaAs会被蚀刻,由此引发崩边并对器件性能及可靠性造成不利影响。本文中,用于通孔蚀刻的GaAs厚度不小于200 μm,通孔边缘没有被蚀刻的痕迹,以实现金属导线的平滑连接。采用光阻和金属来充当掩膜,有效解决了单一光阻因厚度过高而变形或者厚度薄导致GaAs衬底被蚀刻的问题。通过优化工艺,在光阻厚度为32 μm、金属掩膜厚度为0.5 μm、金属蚀刻时间为60 s以及感应耦合等离子体(Inductively Couple Plasma, ICP)蚀刻4000 s的条件下,得到了孔深为200 μm且通孔边缘平整的形貌。分析了 GaAs 崩边形成的主要原因与机理,并通过优化工艺解决了200 μm通孔的崩边问题,从而提高了器件性能及可靠性。     

沟槽型VDMOS的重离子辐射失效研究

空间辐射环境中含有各种高能带电粒子,高能带电粒子与电子器件相互作用可能引发单粒子效应（SEE）,单粒子效应中单粒子烧毁（SEB）和单粒子栅穿（SEGR）是两种最主要的单粒子事件。对重离子环境下的器件退化和失效进行了研究,分析了重离子环境下的失效机理,提出了重离子条件下的器件改善结构,同时完成了仿真和重离子实验验证,提升了MOSFET抗重离子能力。