The molecular crystal of oxalyl dihydrazide differentiates into five polymorphs that are governed by inter- and intramolecular hydrogen bonds. The complex mixture of such interactions with long range dispersive forces makes its computational characterization very challenging; thus it represents an ideal benchmark for ab initio methods when striving for a description of polymorphism in molecular crystals. Indeed, a complete experimental energetic profile of this system is still lacking, and it is here investigated by means of periodic dispersion-corrected DFT and Local second order Møller–Plesset Perturbation theory (LMP2) calculations. In this work, the empirical dispersion correction schemes proposed by Tkatchenko and Scheffler (TS) [Tkatchenko et al., Phys. Rev. Lett., 2009, 102, 073005] and Grimme (D2) [Grimme, J. Comput. Chem., 2006, 27, 1787] have been used in combination with the PBE semilocal functional for geometry optimizations. We observed that PBE-TS provides a remarkable improvement in predicting the crystal structure of oxalyl dihydrazide polymorphs with respect to commonly used DFT-D functionals. The relative stabilities of the five forms have then been computed at the PBE-TS/D2, PBE0-D2, B3LYP-D2 and B3LYP-D3(BJ)+gCP level on the PBE-TS hydrogen-optimized geometries and benchmarked against high level periodic LMP2 calculations. PBE-TS, B3LYP-D2 and B3LYP-D3(BJ)+E(3) (that is including three-body corrections) achieve good predictions of the stability ordering, though the broadness of the energy range is slightly larger than in the case of LMP2.

Oxalyl Dihydrazide Polymorphism: a Periodic Dispersion-Corrected DFT and MP2 Investigation / Presti, Davide; Pedone, Alfonso; Menziani, Maria Cristina; B., Civalleri; Lorenzo, Maschio. - In: CRYSTENGCOMM. - ISSN 1466-8033. - ELETTRONICO. - 16:(2014), pp. 102-109. [10.1039/c3ce41758a]

Oxalyl Dihydrazide Polymorphism: a Periodic Dispersion-Corrected DFT and MP2 Investigation.

PRESTI, DAVIDE;PEDONE, Alfonso;MENZIANI, Maria Cristina;
2014

Abstract

The molecular crystal of oxalyl dihydrazide differentiates into five polymorphs that are governed by inter- and intramolecular hydrogen bonds. The complex mixture of such interactions with long range dispersive forces makes its computational characterization very challenging; thus it represents an ideal benchmark for ab initio methods when striving for a description of polymorphism in molecular crystals. Indeed, a complete experimental energetic profile of this system is still lacking, and it is here investigated by means of periodic dispersion-corrected DFT and Local second order Møller–Plesset Perturbation theory (LMP2) calculations. In this work, the empirical dispersion correction schemes proposed by Tkatchenko and Scheffler (TS) [Tkatchenko et al., Phys. Rev. Lett., 2009, 102, 073005] and Grimme (D2) [Grimme, J. Comput. Chem., 2006, 27, 1787] have been used in combination with the PBE semilocal functional for geometry optimizations. We observed that PBE-TS provides a remarkable improvement in predicting the crystal structure of oxalyl dihydrazide polymorphs with respect to commonly used DFT-D functionals. The relative stabilities of the five forms have then been computed at the PBE-TS/D2, PBE0-D2, B3LYP-D2 and B3LYP-D3(BJ)+gCP level on the PBE-TS hydrogen-optimized geometries and benchmarked against high level periodic LMP2 calculations. PBE-TS, B3LYP-D2 and B3LYP-D3(BJ)+E(3) (that is including three-body corrections) achieve good predictions of the stability ordering, though the broadness of the energy range is slightly larger than in the case of LMP2.
2014
16
102
109
Oxalyl Dihydrazide Polymorphism: a Periodic Dispersion-Corrected DFT and MP2 Investigation / Presti, Davide; Pedone, Alfonso; Menziani, Maria Cristina; B., Civalleri; Lorenzo, Maschio. - In: CRYSTENGCOMM. - ISSN 1466-8033. - ELETTRONICO. - 16:(2014), pp. 102-109. [10.1039/c3ce41758a]
Presti, Davide; Pedone, Alfonso; Menziani, Maria Cristina; B., Civalleri; Lorenzo, Maschio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/998515
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