TY - JOUR

T1 - Comprehensive density functional theory studies of vibrational spectra of carbonates

AU - Zhuravlev, Yurii N.

AU - Atuchin, Victor V.

N1 - Funding Information: Funding: This work was supported by the Russian Science Foundation (project 19-42-02003, in the part of conceptualization), Ministry of Science and Higher Education of Russia (project 075-15-2020-797 (13.1902.21.0024)) and Kemerovo State University. Publisher Copyright: © 2020 by the authors. Licensee MDPI, Basel, Switzerland. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/11

Y1 - 2020/11

N2 - Within the framework of the density functional theory (DFT) and the hybrid functional B3LYP by means of the CRYSTAL17 program code, the wavenumbers and intensities of normal oscillations of MgCO3, CaCO3, ZnCO3, CdCO3 in the structure of calcite; CaMg(CO3)2, CdMg(CO3)2, CaMn(CO3)2, CaZn(CO3)2 in the structure of dolomite; BaMg(CO3)2 in the structure of the norsethite type; and CaCO3, SrCO3, BaCO3, and PbCO3 in the structure of aragonite were calculated. Infrared absorption and Raman spectra were compared with the known experimental data of synthetic and natural crystals. For lattice and intramolecular modes, linear dependences on the radius and mass of the metal cation are established. The obtained dependences have predictive power and can be used to study solid carbonate solutions. For trigonal and orthorhombic carbonates, the linear dependence of wavenumbers on the cation radius RM (or M–O distance) is established for the infrared in-plane bending mode: 786.2–65.88·RM and Raman in-plane stretching mode: 768.5–53.24·RM, with a correlation coefficient of 0.87.

AB - Within the framework of the density functional theory (DFT) and the hybrid functional B3LYP by means of the CRYSTAL17 program code, the wavenumbers and intensities of normal oscillations of MgCO3, CaCO3, ZnCO3, CdCO3 in the structure of calcite; CaMg(CO3)2, CdMg(CO3)2, CaMn(CO3)2, CaZn(CO3)2 in the structure of dolomite; BaMg(CO3)2 in the structure of the norsethite type; and CaCO3, SrCO3, BaCO3, and PbCO3 in the structure of aragonite were calculated. Infrared absorption and Raman spectra were compared with the known experimental data of synthetic and natural crystals. For lattice and intramolecular modes, linear dependences on the radius and mass of the metal cation are established. The obtained dependences have predictive power and can be used to study solid carbonate solutions. For trigonal and orthorhombic carbonates, the linear dependence of wavenumbers on the cation radius RM (or M–O distance) is established for the infrared in-plane bending mode: 786.2–65.88·RM and Raman in-plane stretching mode: 768.5–53.24·RM, with a correlation coefficient of 0.87.

KW - Cation radius

KW - Density Functional Theory

KW - Infrared spectra

KW - Metal carbonates

KW - Normal vibrations

KW - Raman spectra

KW - CRYSTAL RAMAN-SPECTROSCOPY

KW - AB-INITIO

KW - HIGH-TEMPERATURE

KW - HIGH-PRESSURE BEHAVIOR

KW - SOLID-SOLUTION

KW - normal vibrations

KW - infrared spectra

KW - RAY PHOTOELECTRON-SPECTROSCOPY

KW - MAGNESITE

KW - metal carbonates

KW - cation radius

KW - PHASE-DIAGRAM

KW - ELECTRONIC-STRUCTURE

KW - ARAGONITE

UR - http://www.scopus.com/inward/record.url?scp=85096229830&partnerID=8YFLogxK

U2 - 10.3390/nano10112275

DO - 10.3390/nano10112275

M3 - Article

C2 - 33212956

AN - SCOPUS:85096229830

VL - 10

SP - 1

EP - 19

JO - Nanomaterials

JF - Nanomaterials

SN - 2079-4991

IS - 11

M1 - 2275

ER -