1. Spectroscopic analysis in molecular simulations with discretized Wiener-Khinchin theorem for Fourier-Laplace transformation
- Author
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Takashi Yamamoto, Koji Fukao, Akira Koyama, David A. Nicholson, Marat Andreev, and Gregory C. Rutledge
- Subjects
Physics ,Discretization ,Laplace transform ,Autocorrelation ,Mathematical analysis ,Function (mathematics) ,Wiener–Khinchin theorem ,01 natural sciences ,010305 fluids & plasmas ,symbols.namesake ,Fourier transform ,Transformation (function) ,0103 physical sciences ,symbols ,Relaxation (approximation) ,010306 general physics - Abstract
The Wiener-Khinchin theorem for the Fourier-Laplace transformation (WKT-FLT) provides a robust method to obtain the single-side Fourier transforms of arbitrary time-domain relaxation functions (or autocorrelation functions). Moreover, by combining an on-the-fly algorithm with the WKT-FLT, the numerical calculations of various complex spectroscopic data in a wide frequency range become significantly more efficient. However, the discretized WKT-FLT equation, obtained simply by replacing the integrations with the discrete summations, always produces two artifacts in the frequency-domain relaxation function. In addition, the artifacts become more apparent in the frequency-domain response function converted from the relaxation function. We find the sources of these artifacts that are associated with the discretization of the WKT-FLT equation. Taking these sources into account, we derive discretized WKT-FLT equations designated for both the frequency-domain relaxation and response functions with the artifacts removed. The use of the discretized WKT-FLT equations with the on-the-fly algorithm is illustrated by a flow chart. We also give application examples for the wave-vector-dependent dynamic susceptibility in an isotropic amorphous polyethylene and the frequency-domain response functions of the orientation vectors in an $n$-alkane crystal.
- Published
- 2020
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