2. 数据后处理实例_Zier_ABS data

Agilent CrysAlisPro 数据后处理实例 严子耳 博士 安捷伦科技XRD产品应用工程师 结冰 晶体移动 背景异常 吸收校正 2 Agilent Confidential 4/23/2013 实例一: 结冰 样品详情 100 μm Sample measurements: 0.053 x 0.141 x 0.169 mm Monoclinic, P21/n a = 9.5360(3)Å , b = 11.8287(4)Å , c = 29.9258(8)Å α = 90°, β = 96.623(3) °, γ = 90° Reference Rint = 2.60% Reference R1 = 3.83% Icy sample Rint = 10.50% Icy sample R1 = 6.11% 3 Agilent Confidential 4/23/2013 实例一: 结冰 衍射照片 • 很明显的杂点. • 形成冰环 4 Agilent Confidential 4/23/2013 实例一: 结冰 参照衍射照片 5 Agilent Confidential 4/23/2013 实例一: 结冰 目测…… 6 Agilent Confidential 4/23/2013 实例一: 结冰 指标化率低 7 Agilent Confidential 4/23/2013 实例一: 结冰 数据还原 高Rint值 奇怪的背景 8 Agilent Confidential 4/23/2013 实例一: 结冰 EwaldPRO 9 Agilent Confidential 4/23/2013 实例一: 结冰 指标化 10 Agilent Confidential 4/23/2013 实例一: 结冰 1. 去掉结冰严重的衍射照片 11 Agilent Confidential 4/23/2013 Refinalisation with filters 实例一: 结冰 1.去掉结冰严重的衍射照片 12 Agilent Confidential 4/23/2013 实例一: 结冰 2. d range filters 13 Agilent Confidential 4/23/2013 实例一: 结冰 2. d range filters 14 Agilent Confidential 4/23/2013 实例一: 结冰 2. d range filters 15 Agilent Confidential 4/23/2013 Page 3 实例一: 结冰 3. Bad profile filter 16 Agilent Confidential 4/23/2013 Reference Data Auto analysis d range and run Filtering Bad profile filtering Rint (%) 2.6 10.5 3.2 4.0 I/σ 17.7 8.4 14.0 12.7 R1 (%) 3.83 6.11 4.11 4.50 Comp (%) 99.9 99.9 92.6 98.6 实例一: 结冰 还原和精修结果 17 Agilent Confidential 4/23/2013 • 取向矩阵改变 • 衍射点位置预测错误 • 指标化率低 • Reference Frames 异常 • Rint 异常高 • I/σ较低 实例二: 晶体移动 18 Agilent Confidential 4/23/2013 Nicotinamide, C6H6N2O Sample measurements: 0.036 x 0.048 x 0.176 mm Monoclinic, P21/c a = 3.9732(2)Å , b = 15.6382(8)Å c = 9.4267(4)Å α = 90°, β = 99.042(4)°, γ = 90° Reference Rint = 1.60% Reference R1 = 3.32% 100μm 实例二: 晶体移动 样品详情－无移动的情况 19 Agilent Confidential 4/23/2013 • 异常的还原结果 • 高Rint • 低信噪比 • 低衍射能力 • 指标化率低 实例二: 晶体移动 现象 20 Agilent Confidential 4/23/2013 • 看上去像是孪晶 • 孪晶指标化率96.8% …孪晶还原结果异常 －不是非缺面孪晶 实例二: 晶体移动 现象 21 Agilent Confidential 4/23/2013 在Run 5 和Run 6之间有明显变化 实例二: 晶体移动 Reference Frames 22 Agilent Confidential 4/23/2013 Run 5 之后的衍射点位置预测有误 实例二: 晶体移动 现象－HKL overlay 23 Agilent Confidential 4/23/2013 实例二: 晶体移动 Check for the sample jumping 24 Agilent Confidential 4/23/2013 实例二: 晶体移动 倒易空间 25 Agilent Confidential 4/23/2013 Step 3 实例二: 晶体移动 手动数据还原 26 Agilent Confidential 4/23/2013 Reference Data Slip Data (Pre- Treatment) Slip Data (Post- Treatment) Rint (%) 1.6 14.7 1.6 I/σ 22.0 5.0 22.9 R1 (%) 3.32 43.88 3.46 Comp (%) 98.5 95.2% 98.4% 实例二: 晶体移动 手动数据还原结果 27 Agilent Confidential 4/23/2013 实例三: 异常的背景 • 原因 • 上样方式不当 • 样品荧光效应等 • 现象 • 高且不均一的背景 • 指标化率低 • I/σ异常低 • Rint 异常高 28 Agilent Confidential 4/23/2013 Theophylline monohydrate, C7H8N4O2, H2O Sample size: 0.036 x 0.049 x 0.129 mm Monoclinic, P21/n a = 4.4809(4) Å , b = 15.3969(13) Å , c = 13.2734(13) Å α = 90°, β = 98.505(9) °, γ = 90° Reference data (to 0.9 Å ) R1 = 5.28 % Rint = 3.10% 100μm 100μm 实例三: 异常的背景 样品详情 29 Agilent Confidential 4/23/2013 • 从衍射照片上发现非常高的 背景。 • 常规寻峰找到很多无法指标 化的衍射峰。 • 指标化困难。 • 数据还原结果差。 实例三: 异常的背景 现象 30 Agilent Confidential 4/23/2013 实例三: 异常的背景 指标化 31 Agilent Confidential 4/23/2013 实例三: 异常的背景 指标化 32 Agilent Confidential 4/23/2013 实例三: 异常的背景 指标化 33 Agilent Confidential 4/23/2013 Page 4 实例三: 异常的背景 数据还原－Smart background 34 Agilent Confidential 4/23/2013 Reference Data Auto analysis Smart Background Diff. Limit 0.92 1.41 0.97 Rint (%) 3.1 14.4 5.8 I/σ 13.5 3.0 7.8 R1 (%) 5.28 - 6.22 Comp (%) 99.5 99.5 99.5 实例三: 异常的背景 数据处理结果 35 Agilent Confidential 4/23/2013 实例四:吸收校正 Mu值 mu(mm-1) 43.09 1/mu(mm) 0.023 Size(mm) I(%) 0.02 42.240% 0.04 17.842% 0.06 7.537% 0.08 3.183% 0.1 1.345% 0.12 0.568% 0.14 0.240% 0.16 0.101% 0.18 0.043% 0.2 0.018% Iout=Iorg*exp(-mu*size) 36 Agilent Confidential 4/23/2013 晶体太大 →Total absorption 实例四:吸收校正 三类方法 • Abspack －Multi-Scan 经验吸收校正 ,默认设置 • Face indexing 晶面指标化吸收校正 • Spherical abs 球形吸收校正 37 Agilent Confidential 4/23/2013 实例四:吸收校正 校正方法 使用条件 Abspack 默认设置 Abspack + spherical abs mu>5mm-1 Face indexing Any mu Abspack+face indexing Any mu Spherical abs Theta decay for very strong absorbers, mu>30mm-1 请不要在Abspack+face indexing的基础上加用Spherical abs！ Overcorrect！ 38 Agilent Confidential 4/23/2013 实例四:吸收校正 Method Rint(%) R1(%) wR2(%) Highest Peak Deepest Peak ABS+Face- index 3.48 1.54 3.15 0.90 -1.19 分子式: Pb4{Co2[B(OH)2P2O8](PO4)2}Cl; a=9.73895(18) b=9.73895(18) c=90.9391(18) alpha=90 beta=90 gamma=120; 光源: 钼 ; mu: 43.09 mm-1; The sample is from Dr Miao Yang in Dalian Institute of Chemical Physics, CAS 晶体大小:0.08×0.06×0.02 mm 扫描宽度: 0.2º 检测器距离: 100mm 曝光时间: 1s/4s 39 Agilent Confidential 4/23/2013 实例四:吸收校正 Method Rint(%) Mean F2 R1(%) wR2(%) Highest Peak Deepest Peak Weight Ueq of W3 (Å2×103) ABSpack 4.5 33799.07 11.06 28.55 10.42 -15.21 0.2 0.8(3) ABS+Face-index 3.5 638095.73 2.99 7.14 3.75 -1.25 0.0349 43.3534 10.7(8) Overcorrected ABS+Face- index+Spherical 3.3 16722833.14 5.58 13.82 3.42 -1.11 0.0963 5.7343 36.18(13) 光源: 铜 mu: 46.03mm-1; 4,4’-联吡啶杂化的锰桥联磷钨酸; 晶体大小: 0.25×0.13×0.11 mm. The sample is from Prof Chuande Wu in Zhejiang University 40 Agilent Confidential 4/23/2013 结冰 晶体移动 背景异常 吸收校正 Questions and Answers 41 Agilent Confidential 4/23/2013 Thank you for listening! Find out more at www.agilent.com/chem/xrd 致谢： Dr Fraser White – Yarnton Dr Mathias Meyer – Wroclaw Prof Chuande Wu in Zhejiang University Dr Miao Yang in Dalian Institute of Chemical Physics, CAS 42