What Is More Important When Calculating the Thermodynamic Properties of Organic Crystals, Density Functional, Supercell, or Energy Second-Order Derivative Method Choice? | Sciact - CRIS-system of Boreskov Institute of Catalysis

What Is More Important When Calculating the Thermodynamic Properties of Organic Crystals, Density Functional, Supercell, or Energy Second-Order Derivative Method Choice? Full article

Journal

Crystals
, E-ISSN: 2073-4352

Output data

Year: 2025, Volume: 15, Number: 3, Article number : 274, Pages count : 17 DOI: 10.3390/cryst15030274

Tags

thermodynamic properties; energy second-order derivatives; pyrazinamide; DFPT; finite-difference approach; supercell; functional choice; dispersion correction; benchmarking; polymorphism

Authors

Dubok Aleksandr S. ^1,2 , Rychkov Denis A. ^1,3

Affiliations

1	Institute of Solid State Chemistry and Mechanochemistry SB RAS, 630090 Novosibirsk, Russia
2	Laboratory of Physicochemical Fundamentals of Pharmaceutical Materials, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia
3	SRF “SKIF”, Boreskov Institute of Catalysis, 630559 Koltsovo, Russia

Calculation of second-order derivatives of energy using the DFT method is a valuable approach for the estimation of both the thermodynamical and mechanical properties of organic crystals from the first principles. This type of calculation requires specification of several computational parameters, including the functional, supercell, and method of phonon calculations. Nevertheless, the importance of these parameters is presented in the literature very modestly. In this work, we demonstrate the influence of these computational parameters on the accuracy of calculated second-order derivatives using the practical example of pyrazinamide polymorphs, including the plastically bending α form and the β, γ, and brittle δ form. The effects of the settings used on the resulting enthalpies of the polymorphic modifications of pyrazinamide are compared: supercell setting (primitive cell vs. appropriate supercell) has a much stronger impact than functional (PBE-D3BJ vs. Hamada rev-vdW-DF2) which in turn affects results significantly more than the method for second-order derivative computation (FD vs. DFPT approach). Finally, we propose some suggestions for choosing the right settings for calculating second-order derivatives for molecular crystals.

Dubok A.S. , Rychkov D.A.
What Is More Important When Calculating the Thermodynamic Properties of Organic Crystals, Density Functional, Supercell, or Energy Second-Order Derivative Method Choice?
Crystals. 2025. V.15. N3. 274 :1-17. DOI: 10.3390/cryst15030274 WOS Scopus OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Jan 28, 2025
Accepted:	Mar 13, 2025
Published online:	Mar 16, 2025

Web of science:	WOS:001451968400001
Scopus:	2-s2.0-105001431618
OpenAlex:	W4408529775
publication_identifier.sciact_skif_identifier_type:	3813

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