Ab initio modeling of Raman and infrared spectra of calcite
Kalinin N.V., Saleev V.A.

Samara National Research University, Samara, Russia

Calcite is the most thermodynamically stable polymorphic phase of the CaCO3 crystal. It is widely used in modern optical instruments operating in the infrared and visible wavelengths of electromagnetic radiation. In particular, due to its anisotropic properties, calcite is used in polarization optics devices. Ab initio quantum mechanical modeling of the Raman and infrared spectra of calcite makes it possible to better understand the structure and nature of the chemical bonds of the compound, and find the optimal conditions for the effective use of unique properties of calcite in photonics tools. The calculations are performed within the framework of the density functional theory in the CRYSTAL program, using the “hybrid” B3LYP functional and the all-electronic bases of the STO-6G, PO-TZVP and BSD atomic orbitals of the Gaussian type. The obtained results for the elastic constants, Raman and infrared spectra of calcite agree satisfactorily with the available experimental data for the basic sets of POB-TZVP and BSD.

Ключевые слова:
photonics; calcite; IR spectrum; Raman spectrum; ab initio modeling; density functional theory; hybrid functional.

Kalinin NV, Saleev VA. Ab initio modeling of Raman and infrared spectra of calcite. Computer Optics 2018; 42(2): 263-266. DOI: 10.18287/2412-6179-2018-42-2-263-266.


  1. Hohenberg P, Kohn W. Inhomogeneous electron gas. Phys Rev 1964; 136(3B): B864-B871. DOI: 10.1103/PhysRev.36.B864.
  2. Decius JC, Hexter RM. Molecular vibrations in crystals. New York: McGraw-Hill; 1977. ISBN: 978-0-0702861-5.
  3. Maschio L, Kirtman B, Rérat M,Orlando R, Dovesi R. Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock or Kohn-Sham method in anatomic orbital basis. J Chem Phys 2013; 139(16): 164101. DOI: 10.1063/1.4824442.
  4. De La Pierre M, Carteret C, Maschio L, André E, Orlando R, Dovesi R. The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study. J Chem Phys 2014; 140(16): 164509. DOI: 10.1063/1.4871900.
  5. Carteret C, De La Pierre M, Dossot M, Pascale F, Erba A. The vibrational spectrum of CaCO3 aragonite: A combined experimental and quantum-mechanical investigation. J Chem Phys 2013; 138(1): 014201. DOI: 10.1063/1.4772960.
  6. Becke AD. Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 1993; 98(7): 5648-5652. DOI: 10.1063/1.464913.
  7. Pencipe M, Pascale F, Zicovich-Wilson CM, Saunders VR, Orlando R, Dovesi R. The vibration spectrum of calcite (CaCO3): Ab initio quantum mechanical calculations. Physics and Chemistry of Minerals 2004; 31(8): 559-564. DOI: 10.1007/s00269-004-0418-7.
  8. Catti M, Pavese A, Dovesi R, Saunders VC. Static lattice and electron properties of MgCO3 (Magnesite) calculated by ab initio periodic Hartree-Fock methods. Phys Rev B 1993; 47(15): 9189-9198. DOI: 10.1103/PhysRevB.47.9189.
  9. Peintinger MF, Oliveira DV, Bredow T. Consistent gaussian basis sets of triple-zeta valence with polarization quality for solid-state calculations. J Comp Chem 2013; 34(6): 451-459. DOI: 10.1002/jcc.23153.
  10. Valenzano L, Torres FJ, Doll K, Pascale F, Zicovich-Wilson CM, Dovesi R. Ab initio study of the vibrational spectrum and related properties of crystalline compaunds: the case of CaCO3 calcite. Zeitschrift für Physikalische Chemie 2006; 220(7/2006): 893-912. DOI: 10.1524/zpch.2006.220.7.893.
  11. Hill R. The elastic behaviour of a crystalline aggregate. Proc Phys Soc A 1952; 65(5): 349-354. DOI: 10.1088/0370-1298/65/5/307.
  12. Dandekar DP. Elastic constants of calcite. J Appl Phys 1968; 39(6): 2971-2973. DOI: 10.1063/1.1656709.
  13. Dovesi R, Orlando R, Erba A, Zicovich?Wilson CM, Casassa BCS, Maschio L, Ferrabone M, De La Pierre M, D'Arco P, Causà YNM, Rérat M, Kirtman B. CRYSTAL14: A program for the ab initio investigation of crystalline solids. Int J Quantum Chem 2014: 114(19): 1287-1317. DOI: 10.1002/qua.24658.

© 2009, IPSI RAS
Россия, 443001, Самара, ул. Молодогвардейская, 151; электронная почта: ko@smr.ru ; тел: +7 (846) 242-41-24 (ответственный секретарь), +7 (846) 332-56-22 (технический редактор), факс: +7 (846) 332-56-20