Statistical analysis of second harmonic generation experiments: a phenomenological model

Welsh, Alan H., Mansson, Ralph A., Frey, Jeremy G. and Danos, Lefteris (2005) Statistical analysis of second harmonic generation experiments: a phenomenological model Chemometrics and Intelligent Laboratory Systems, 75, (1), pp. 45-54. (doi:10.1016/j.chemolab.2004.05.002).


Full text not available from this repository.


We discuss issues arising in fitting theoretically derived nonlinear models with complex coefficients to data from surface Second Harmonic Generation (SHG) experiments conducted at the air/liquid interface. We explore different parametrisations for the complex parameters and show that the Enter (magnitude and phase angle) parametrisation is preferable to the real and imaginary parts parametrisation, both theoretically and empirically. We emphasise the importance and value of diagnostic plots for evaluating the quality of model fit. We derive approximate standard errors for the parameter estimates and discuss issues of making inference about ratios of parameters. We consider approximate confidence intervals (using the approximate standard errors), profile likelihood intervals, Fieller's method and bootstrap intervals. Fieller's method (and the bootstrap intervals) provide useful information on the value of the simpler approximate confidence intervals. We also propose and implement a likelihood ratio test to assess whether a common model can be fitted to several independent data sets. Finally, the methods are applied to data sets obtained from SHG experiments on L-phenylalanine at the air/water interface and toluene.

Item Type: Article
Digital Object Identifier (DOI): doi:10.1016/j.chemolab.2004.05.002
Keywords: complex coefficients, confidence intervals, likelihood ratio test, nonlinear least squares, ratios of parameters

ePrint ID: 20930
Date :
Date Event
28 January 2005Published
Date Deposited: 01 Mar 2006
Last Modified: 16 Apr 2017 22:58
Further Information:Google Scholar

Actions (login required)

View Item View Item