Spectroscopic analysis in molecular simulations with discretized Wiener-Khinchin theorem for Fourier-Laplace transformation.

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.