GENERALIZED RANK ANNIHILATION METHOD .2. BIAS AND VARIANCE IN THE ESTIMATED EIGENVALUES

被引:30
作者
FABER, NM
BUYDENS, LMC
KATEMAN, G
机构
[1] Department of Analytical Chemistry, University of Nijmegen, Nijmegen, 6525 ED
关键词
RAFA; GRAM; EIGENVALUES; BIAS; VARIANCE;
D O I
10.1002/cem.1180080303
中图分类号
TP [自动化技术、计算机技术];
学科分类号
0812 ;
摘要
Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this second paper expressions are derived for predicting the bias and variance in the eigenvalues of GRAM. These expressions are built on the analogies between a reformulation of the eigenvalue problem and the prediction equations of univariate and multivariate calibration. The error analysis will also be performed for Lorber's formulation of RAFA. It will be demonstrated that, depending on the size of the eigenvalue, large differences in performance must be expected. A bias correction technique is proposed that effectively eliminates the bias if the error in the bias estimate is not too large. The derived expressions are evaluated by Monte Carlo simulations. It is shown that the predictions are satisfactory up to the limit of detection. The results are not sensitive to an incorrect choice of the dimension of the factor space.
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页码:181 / 203
页数:23
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