First-Principle Studies of the Vibrational Properties of Carbonates under Pressure
Using the density functional theory with the hybrid functional B3LYP and the basis of localized orbitals of the CRYSTAL17 program code, the dependences of the wavenumbers of normal long-wave <i>ν</i> vibrations on the <i>P</i>(GPa) pressure <i>ν</i>(cm<sup>−...
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MDPI AG
2021-05-01
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| Series: | Sensors |
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| Online Access: | https://www.mdpi.com/1424-8220/21/11/3644 |
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| author | Yurii N. Zhuravlev Victor V. Atuchin |
| author_facet | Yurii N. Zhuravlev Victor V. Atuchin |
| author_sort | Yurii N. Zhuravlev |
| collection | DOAJ |
| description | Using the density functional theory with the hybrid functional B3LYP and the basis of localized orbitals of the CRYSTAL17 program code, the dependences of the wavenumbers of normal long-wave <i>ν</i> vibrations on the <i>P</i>(GPa) pressure <i>ν</i>(cm<sup>−1</sup>) = <i>ν</i><sub>0</sub> + (<i>dv</i>/<i>dP</i>)·<i>P</i> + (<i>d</i><sup>2</sup><i>v</i>/<i>dP</i><sup>2</sup>)·<i>P</i> and structural parameters <i>R</i>(Å) (<i>R</i>: <i>a</i>, <i>b</i>, <i>c</i>, <i>R</i><sub>M-O</sub>, <i>R</i><sub>C-O</sub>): <i>ν</i>(cm<sup>−1</sup>) = <i>ν</i><sub>0</sub> + (<i>dv</i>/<i>dR</i>) − (<i>R</i> − <i>R</i><sub>0</sub>) were calculated. Calculations were made for crystals with the structure of calcite (MgCO<sub>3</sub>, ZnCO<sub>3</sub>, CdCO<sub>3</sub>), dolomite (CaMg(CO<sub>3</sub>)<sub>2</sub>, CdMg(CO<sub>3</sub>)<sub>2</sub>, CaZn(CO<sub>3</sub>)<sub>2</sub>) and aragonite (SrCO<sub>3</sub>, BaCO<sub>3</sub>, PbCO<sub>3</sub>). A comparison with the experimental data showed that the derivatives can be used to determine the <i>P</i> pressures, <i>a</i>, <i>b</i>, <i>c</i> lattice constants and the <i>R</i><sub>M-O</sub> metal-oxygen, and the <i>R</i><sub>C-O</sub> carbon-oxygen interatomic distances from the known Δ<i>ν</i> shifts. It was found that, with the increasing pressure, the lattice constants and distances <i>R</i> decrease, and the wavenumbers increase with velocities the more, the higher the <i>ν</i><sub>0</sub> is. The exceptions were individual low-frequency lattice modes and out-of-plane vibrations of the <i>v</i><sub>2</sub>-type carbonate ion, for which the dependences are either nonlinear or have negative <i>dv/dP</i> (positive <i>dv</i>/<i>dR</i>) derivatives. The reason for this lies in the properties of chemical bonding and the nature of atomic displacements during these vibrations, which cause a decrease in <i>R</i><sub>M-O</sub> and an increase in <i>R</i><sub>C-O</sub>. |
| first_indexed | 2024-03-10T11:06:57Z |
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| institution | Directory Open Access Journal |
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| language | English |
| last_indexed | 2024-03-10T11:06:57Z |
| publishDate | 2021-05-01 |
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| series | Sensors |
| spelling | doaj.art-fd081976721f424793b3b3f05b19dd542023-11-21T21:07:07ZengMDPI AGSensors1424-82202021-05-012111364410.3390/s21113644First-Principle Studies of the Vibrational Properties of Carbonates under PressureYurii N. Zhuravlev0Victor V. Atuchin1Institute of Basic Sciences, Kemerovo State University, 650000 Kemerovo, RussiaResearch and Development Department, Kemerovo State University, 650000 Kemerovo, RussiaUsing the density functional theory with the hybrid functional B3LYP and the basis of localized orbitals of the CRYSTAL17 program code, the dependences of the wavenumbers of normal long-wave <i>ν</i> vibrations on the <i>P</i>(GPa) pressure <i>ν</i>(cm<sup>−1</sup>) = <i>ν</i><sub>0</sub> + (<i>dv</i>/<i>dP</i>)·<i>P</i> + (<i>d</i><sup>2</sup><i>v</i>/<i>dP</i><sup>2</sup>)·<i>P</i> and structural parameters <i>R</i>(Å) (<i>R</i>: <i>a</i>, <i>b</i>, <i>c</i>, <i>R</i><sub>M-O</sub>, <i>R</i><sub>C-O</sub>): <i>ν</i>(cm<sup>−1</sup>) = <i>ν</i><sub>0</sub> + (<i>dv</i>/<i>dR</i>) − (<i>R</i> − <i>R</i><sub>0</sub>) were calculated. Calculations were made for crystals with the structure of calcite (MgCO<sub>3</sub>, ZnCO<sub>3</sub>, CdCO<sub>3</sub>), dolomite (CaMg(CO<sub>3</sub>)<sub>2</sub>, CdMg(CO<sub>3</sub>)<sub>2</sub>, CaZn(CO<sub>3</sub>)<sub>2</sub>) and aragonite (SrCO<sub>3</sub>, BaCO<sub>3</sub>, PbCO<sub>3</sub>). A comparison with the experimental data showed that the derivatives can be used to determine the <i>P</i> pressures, <i>a</i>, <i>b</i>, <i>c</i> lattice constants and the <i>R</i><sub>M-O</sub> metal-oxygen, and the <i>R</i><sub>C-O</sub> carbon-oxygen interatomic distances from the known Δ<i>ν</i> shifts. It was found that, with the increasing pressure, the lattice constants and distances <i>R</i> decrease, and the wavenumbers increase with velocities the more, the higher the <i>ν</i><sub>0</sub> is. The exceptions were individual low-frequency lattice modes and out-of-plane vibrations of the <i>v</i><sub>2</sub>-type carbonate ion, for which the dependences are either nonlinear or have negative <i>dv/dP</i> (positive <i>dv</i>/<i>dR</i>) derivatives. The reason for this lies in the properties of chemical bonding and the nature of atomic displacements during these vibrations, which cause a decrease in <i>R</i><sub>M-O</sub> and an increase in <i>R</i><sub>C-O</sub>.https://www.mdpi.com/1424-8220/21/11/3644calcitedolomitearagonitepressurevibrational spectroscopyhydrostaticity |
| spellingShingle | Yurii N. Zhuravlev Victor V. Atuchin First-Principle Studies of the Vibrational Properties of Carbonates under Pressure Sensors calcite dolomite aragonite pressure vibrational spectroscopy hydrostaticity |
| title | First-Principle Studies of the Vibrational Properties of Carbonates under Pressure |
| title_full | First-Principle Studies of the Vibrational Properties of Carbonates under Pressure |
| title_fullStr | First-Principle Studies of the Vibrational Properties of Carbonates under Pressure |
| title_full_unstemmed | First-Principle Studies of the Vibrational Properties of Carbonates under Pressure |
| title_short | First-Principle Studies of the Vibrational Properties of Carbonates under Pressure |
| title_sort | first principle studies of the vibrational properties of carbonates under pressure |
| topic | calcite dolomite aragonite pressure vibrational spectroscopy hydrostaticity |
| url | https://www.mdpi.com/1424-8220/21/11/3644 |
| work_keys_str_mv | AT yuriinzhuravlev firstprinciplestudiesofthevibrationalpropertiesofcarbonatesunderpressure AT victorvatuchin firstprinciplestudiesofthevibrationalpropertiesofcarbonatesunderpressure |