Identifying surface phonons in the vibrational spectra of carbonated apatite using density functional theory

Aleksandar Živković; Dejan Gemeri; Hilke Bahmann; Igor Lukačević; Helen E. King

doi:10.1016/j.mtcomm.2023.106596

Identifying surface phonons in the vibrational spectra of carbonated apatite using density functional theory

Aleksandar Živković^*
, Dejan Gemeri
, Hilke Bahmann
, Igor Lukačević
, Helen E. King

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Vibrational spectroscopy is widely used to examine the mineralogy of bone apatite. Yet, these spectra may be significantly influenced by the nanometre size of the crystallites through either phonon confinement or surface phonon contributions. This could lead to misinterpretations of the implications of non-apatitic environments that have been described previously as additional bands in the vibrational spectra. Here we use density functional theory to simulate bulk and slabs of hydroxyapatite as well as A-type, B-type, and AB-type carbonated apatite to test for eventual contributions of surface phonons. The analysis showed that surface phonons can have a significant intensity in the vibrational spectra. They are expected at both higher and lower wavenumbers than their bulk counterparts, unlike phonon confinement which has been linked with only lower wavenumber shifts. The band shift of surface phonons was up to 40 cm⁻¹, which is determinable by both Raman and Infrared spectroscopy. All internal modes of evaluated molecular groups (OH, CO₃, PO₄) were affected by the surface presence. Therefore, it is expected that surface phonons are likely to be present in the vibrational spectra of bone minerals and contribute to spectral effects such as line broadening, presenting a crucial factor in their interpretation and application.

Original language	English
Article number	106596
Pages (from-to)	1-14
Number of pages	14
Journal	Materials Today Communications
Volume	36
DOIs	https://doi.org/10.1016/j.mtcomm.2023.106596
Publication status	Published - Aug 2023

Bibliographical note

Funding Information:
The work described here was performed with the support of the EC Research Innovation Action under the H2020 Programme under the Project HPC-EUROPA3 ( INFRAIA-2016-1-730897 ). The authors would particularly like to acknowledge the support of Department of Earth Sciences, Utrecht University, Netherlands and the computer resources and technical support provided by SURFsara.

Publisher Copyright:
© 2023 The Authors

Funding

The work described here was performed with the support of the EC Research Innovation Action under the H2020 Programme under the Project HPC-EUROPA3 ( INFRAIA-2016-1-730897 ). The authors would particularly like to acknowledge the support of Department of Earth Sciences, Utrecht University, Netherlands and the computer resources and technical support provided by SURFsara.

Funders	Funder number
EC Research Innovation Action	INFRAIA-2016-1-730897
Department of Earth Sciences, Utrecht University, Netherlands

Keywords

Bone
Carbonated apatite
Density functional theory
Infrared spectroscopy
Raman spectroscopy
Surface phonons

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Cite this

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title = "Identifying surface phonons in the vibrational spectra of carbonated apatite using density functional theory",

abstract = "Vibrational spectroscopy is widely used to examine the mineralogy of bone apatite. Yet, these spectra may be significantly influenced by the nanometre size of the crystallites through either phonon confinement or surface phonon contributions. This could lead to misinterpretations of the implications of non-apatitic environments that have been described previously as additional bands in the vibrational spectra. Here we use density functional theory to simulate bulk and slabs of hydroxyapatite as well as A-type, B-type, and AB-type carbonated apatite to test for eventual contributions of surface phonons. The analysis showed that surface phonons can have a significant intensity in the vibrational spectra. They are expected at both higher and lower wavenumbers than their bulk counterparts, unlike phonon confinement which has been linked with only lower wavenumber shifts. The band shift of surface phonons was up to 40 cm−1, which is determinable by both Raman and Infrared spectroscopy. All internal modes of evaluated molecular groups (OH, CO3, PO4) were affected by the surface presence. Therefore, it is expected that surface phonons are likely to be present in the vibrational spectra of bone minerals and contribute to spectral effects such as line broadening, presenting a crucial factor in their interpretation and application.",

keywords = "Bone, Carbonated apatite, Density functional theory, Infrared spectroscopy, Raman spectroscopy, Surface phonons",

author = "Aleksandar {\v Z}ivkovi{\'c} and Dejan Gemeri and Hilke Bahmann and Igor Luka{\v c}evi{\'c} and King, \{Helen E.\}",

note = "Funding Information: The work described here was performed with the support of the EC Research Innovation Action under the H2020 Programme under the Project HPC-EUROPA3 ( INFRAIA-2016-1-730897 ). The authors would particularly like to acknowledge the support of Department of Earth Sciences, Utrecht University, Netherlands and the computer resources and technical support provided by SURFsara. Publisher Copyright: {\textcopyright} 2023 The Authors",

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AU - Živković, Aleksandar

AU - Gemeri, Dejan

AU - Bahmann, Hilke

AU - Lukačević, Igor

AU - King, Helen E.

N1 - Funding Information: The work described here was performed with the support of the EC Research Innovation Action under the H2020 Programme under the Project HPC-EUROPA3 ( INFRAIA-2016-1-730897 ). The authors would particularly like to acknowledge the support of Department of Earth Sciences, Utrecht University, Netherlands and the computer resources and technical support provided by SURFsara. Publisher Copyright: © 2023 The Authors

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N2 - Vibrational spectroscopy is widely used to examine the mineralogy of bone apatite. Yet, these spectra may be significantly influenced by the nanometre size of the crystallites through either phonon confinement or surface phonon contributions. This could lead to misinterpretations of the implications of non-apatitic environments that have been described previously as additional bands in the vibrational spectra. Here we use density functional theory to simulate bulk and slabs of hydroxyapatite as well as A-type, B-type, and AB-type carbonated apatite to test for eventual contributions of surface phonons. The analysis showed that surface phonons can have a significant intensity in the vibrational spectra. They are expected at both higher and lower wavenumbers than their bulk counterparts, unlike phonon confinement which has been linked with only lower wavenumber shifts. The band shift of surface phonons was up to 40 cm−1, which is determinable by both Raman and Infrared spectroscopy. All internal modes of evaluated molecular groups (OH, CO3, PO4) were affected by the surface presence. Therefore, it is expected that surface phonons are likely to be present in the vibrational spectra of bone minerals and contribute to spectral effects such as line broadening, presenting a crucial factor in their interpretation and application.

AB - Vibrational spectroscopy is widely used to examine the mineralogy of bone apatite. Yet, these spectra may be significantly influenced by the nanometre size of the crystallites through either phonon confinement or surface phonon contributions. This could lead to misinterpretations of the implications of non-apatitic environments that have been described previously as additional bands in the vibrational spectra. Here we use density functional theory to simulate bulk and slabs of hydroxyapatite as well as A-type, B-type, and AB-type carbonated apatite to test for eventual contributions of surface phonons. The analysis showed that surface phonons can have a significant intensity in the vibrational spectra. They are expected at both higher and lower wavenumbers than their bulk counterparts, unlike phonon confinement which has been linked with only lower wavenumber shifts. The band shift of surface phonons was up to 40 cm−1, which is determinable by both Raman and Infrared spectroscopy. All internal modes of evaluated molecular groups (OH, CO3, PO4) were affected by the surface presence. Therefore, it is expected that surface phonons are likely to be present in the vibrational spectra of bone minerals and contribute to spectral effects such as line broadening, presenting a crucial factor in their interpretation and application.

KW - Bone

KW - Carbonated apatite

KW - Density functional theory

KW - Infrared spectroscopy

KW - Raman spectroscopy

KW - Surface phonons

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JO - Materials Today Communications

JF - Materials Today Communications

M1 - 106596

ER -

Identifying surface phonons in the vibrational spectra of carbonated apatite using density functional theory

Abstract

Bibliographical note

Funding

Keywords

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