title: Infrared Spectroscopy and Born-Oppenheimer Molecular Dynamics Simulation Study on Deuterium Substitution in the Crystalline Benzoic Acid.
abstract: In this study we present complementary computational and experimental studies of hydrogen bond interaction in crystalline benzoic acid and its deuterated and partially deuterated derivatives. The experimental part of the presented work includes preparation of partially deuterated samples and measurement of attenuated total reflection (ATR)-FTIR spectra. Analysis of the geometrical parameters and time course of dipole moment of crystalline benzoic acid and its deuterated and partially deuterated derivatives by Born-Oppenheimer molecular dynamics (BOMD) enabled us to deeply analyze the IR spectra. Presented simulations based on BOMD gave us opportunity to investigate individual motion and its contribution to the IR spectra. The band contours calculated using Fourier transform of autocorrelation function are in quantitative agreement with the experimental spectra. Characterization of single bands was carried out by "normal coordinate analysis". The salient point of our study is a comparison of the spectra of the deuterated and partially deuterated crystalline benzoic acid with that of the nondeuterated one. Furthermore, we have applied the principal component analysis for analysis of the number of components in partially deuterated systems. In this study, we reveal that the arrangements of hydrogen and deuterium atoms in partially deuterated samples are random.
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.
authors.forename: Maciej
authors.initials: M
authors.lastname: Gług
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.|Department of Chemistry, School of Science and Technology, Kwansei Gakuin University , Sanda, Hyogo 669-1337, Japan.
authors.forename: Mateusz Z
authors.identifier: 0000-0002-4686-5400
authors.initials: MZ
authors.lastname: Brela
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.
authors.forename: Marek
authors.initials: M
authors.lastname: Boczar
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.
authors.forename: Andrzej M
authors.initials: AM
authors.lastname: Turek
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.
authors.forename: Łukasz
authors.initials: Ł
authors.lastname: Boda
authors.affiliation: Faculty of Chemistry, Jagiellonian University , 30-060 Kraków, Ingardena 3, Poland.
authors.forename: Marek J
authors.initials: MJ
authors.lastname: Wójcik
authors.affiliation: Advanced Institute for Computational Science, RIKEN , 7-1-26, Minatojima-minami-machi, Chuo-ku, Kobe, Hyogo 650-0047, Japan.
authors.forename: Takahito
authors.initials: T
authors.lastname: Nakajima
authors.affiliation: Department of Chemistry, School of Science and Technology, Kwansei Gakuin University , Sanda, Hyogo 669-1337, Japan.
authors.forename: Yukihiro
authors.initials: Y
authors.lastname: Ozaki