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\begin{document}

\title{Investigation on the stability, electronic, optical and mechanical
properties of novel calcium carbonate hydrates via first-principles
calculations}



\author[1]{Yunxuan Zhou}%
\author[2]{Mingyu Hu}%
\author[3]{Gengsen Xu}%
\author[3]{Ruiju Xu}%
\author[4]{Xiaoyu Chong}%
\author[3]{Jing Feng}%
\affil[1]{Kunming University of Science and Technology,}%
\affil[2]{Faculty of Materials Science and Engineering, Kunming University of Science and Technology}%
\affil[3]{Kunming University of Science and Technology}%
\affil[4]{Pennsylvania State University}%


\vspace{-1em}



  
  \date{May 19, 2024}


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\selectlanguage{english}
\begin{abstract}
Calcium carbonate (CaCO3) is an inorganic compound which is widely used
in industry, chemistry, construction, ocean acidification and
biomineralization due to its rich constituent on earth and excellent
performance, in which calcium carbonate hydrates are important systems.
In Z.Y. Zou et al's work (Science, 2019, 363, 396--400), they found a
novel calcium carbonate hemihydrate phase, but the structure stability,
optical and mechanical properties has not been studied. In this work,
the stability, electronic, optical, and mechanical properties of novel
calcium carbonate hydrates were investigated by using the
first-principles calculations within density functional theory (DFT).
CaCO3\selectlanguage{ngerman}·xH2O (x=1/2, 1 and 6) are determined dynamically stable phases by
phonon spectrum, but the Gibbs energy of reaction of CaCO3·1/2H2O is
higher than other calcium carbonate hydrates. That's why the
CaCO3·1/2H2O is hard to synthesize in the experiments. In addition, the
optical and mechanical properties of CaCO3·xH2O (x=1/2, 1 and 6) are
expounded in detail. It shows that the CaCO3·1/2H2O has the largest bulk
modulus, shear modulus, Young's modulus with the values 60.51, 36.56 and
91.28 GPa with respect to other two calcium carbonate hydrates
investigated in this paper. This work will provide guidance for
experiments and its applications, such as biomineralization, geology,
and industrial processes.%
\end{abstract}\selectlanguage{ngerman}%



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\textbf{}



\textbf{Hosted file}

\verb`Manuscript of CaCO3--INT J QUANTUM CHEM.docx`  available at \url{https://authorea.com/users/288942/articles/414674-investigation-on-the-stability-electronic-optical-and-mechanical-properties-of-novel-calcium-carbonate-hydrates-via-first-principles-calculations}

\textbf{Figures caption}

Fig. 1. The crystal structure of calcium carbonate hydrates;(a)
CaCO\textsubscript{3}\selectlanguage{ngerman}·1/2H\textsubscript{2}O; (b)
CaCO\textsubscript{3}·6H\textsubscript{2}O; (c)
CaCO\textsubscript{3}·H\textsubscript{2}O; (d) The calculated X-ray
diffraction of calcium carbonate hydrates, (e) the calculated X-ray
diffraction of CaCO\textsubscript{3}·1/2H\textsubscript{2}O and
experimental values by Z.Y. Zou et al{[}8{]}

Fig. 2. Phonon dispersion of calcium carbonate hydrates; (a) (b)
CaCO\textsubscript{3}·1/2H\textsubscript{2}O; (c) (d)
CaCO\textsubscript{3}·6H\textsubscript{2}O; (e) (f)
CaCO\textsubscript{3}·H\textsubscript{2}O, the green hollow dots
represent experimental values by Z.Y. Zou et al {[}8{]}

Fig. 3. Band structure and partial density of states of calcium
carbonate hydrates; (a) (b)
CaCO\textsubscript{3}·1/2H\textsubscript{2}O; (c) (d)
CaCO\textsubscript{3}·6H\textsubscript{2}O; (e) (f)
CaCO\textsubscript{3}·H\textsubscript{2}O

Fig. 4. The electric density distribution (a), (c) and (e) and
differences of charge density distribution; (b), (d) and (f) for calcium
carbonate hydrates on the (100) plane; top:
CaCO\textsubscript{3}·H\textsubscript{2}O; middle:
CaCO\textsubscript{3}·6H\textsubscript{2}O; bottom:
CaCO\textsubscript{3}·1/2H\textsubscript{2}O

Fig.5. The optical properties of calcium carbonate hydrates; (a)
Dielectric function; (b) Reflectivity; (c) Conductivity; (d)Absorption;
(e) Refractive index; (f) Loss function.

Fig. 6. Contour plots of the Young's modulus of calcium carbonate
hydrates in 3D space. (a) CaCO\textsubscript{3}·1/2H\textsubscript{2}O;
(b) CaCO\textsubscript{3}·6H\textsubscript{2}O; (c)
CaCO\textsubscript{3}·H\textsubscript{2}O; (d) Planar projections of the
Young's modulus of calcium carbonate hydrates on the (001), (e) (110)
crystallographic planes.

Figure S1. The calculated Mulliken's overlap population of calcium
carbonate hydrates.

(a) CaCO\textsubscript{3}·1/2H\textsubscript{2}O; (b)
CaCO\textsubscript{3}·6H\textsubscript{2}O; (c)
CaCO\textsubscript{3}·H\textsubscript{2}O.

Fig S2.The calculated (a) average bond length (\(\overset{\overline{}}{L}\left(\text{AB}\right)\)(Å))
and (b) the mean bond population (\(\overset{\overline{}}{n}\left(\text{AB}\right)\)(e)) of calcium
carbonate hydrates

Fig. S3. The variations of the elastic moduli (Bulk (\emph{B} ), Shear
(\emph{G} ) and Young moduli (\emph{E} )) value and Poisson's ratio of
calcium carbonate hydrates with different volume.

\textbf{Hosted file}

\verb`Figs of CaCO3 --INT J QUANTUM CHEM.docx`  available at \url{https://authorea.com/users/288942/articles/414674-investigation-on-the-stability-electronic-optical-and-mechanical-properties-of-novel-calcium-carbonate-hydrates-via-first-principles-calculations}

\textbf{Hosted file}

\verb`Tables of CaCO3 --INT J QUANTUM CHEM.docx`  available at \url{https://authorea.com/users/288942/articles/414674-investigation-on-the-stability-electronic-optical-and-mechanical-properties-of-novel-calcium-carbonate-hydrates-via-first-principles-calculations}

\selectlanguage{english}
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