کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
7640540 1494854 2018 6 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Quantum chemical computation-based strategy for alternating least squares initialization in multivariate curve resolution analysis of spectral-pH data
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آنالیزی یا شیمی تجزیه
پیش نمایش صفحه اول مقاله
Quantum chemical computation-based strategy for alternating least squares initialization in multivariate curve resolution analysis of spectral-pH data
چکیده انگلیسی
The main motivation of this work is to provide initial estimates for the initialization of the iterative optimization within the multivariate curve resolution - alternating least squares (MCR-ALS) algorithm for the decomposition of second-order data. It is demonstrated that the combination of quantum chemical calculations with chemometrics constitutes a novel strategy for the ALS initialization in the MCR resolution of pH-modulated chemical data. In this work, the second-order data arise from acid-base experiments of p-nitrophenol (pNP) done under a pH-gradient generated by an automated flow injection (FI) system monitored by UV-vis spectroscopy. The absorption spectra of the species involved in the chemical equilibrium were simulated by means of time-dependent density functional theory (TD-DFT) methods and were utilized to start the ALS optimization. The new approach based on the Tamm-Dancoff-approximation (TDA) CAM-B3LYP method is recommended to obtain the simulated spectra to initialize MCR-ALS, as an alternative to the routinely methods used to generate initial estimates.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Microchemical Journal - Volume 140, July 2018, Pages 183-188
نویسندگان
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