TY - JOUR
T1 - Periodic DFT Computation of Rotational Barriers for Linear Molecules in Zeolites
T2 - Validation via Zero-Point Energies and Isotopic Heat Difference Values of Adsorbed H2/D2
AU - Rybakov, Andrey
AU - Trubnikov, Dmitrii N.
AU - Vercauteren, Daniel
AU - Larin, Alexander
N1 - Funding Information:
The authors thank the Russian Foundation of Basic Research within the grant 20-53-18001 Bolg_а. The research has been carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University [ 88 ].
Funding Information:
The authors thank the Russian Foundation of Basic Research within the grant 20-53-18001 Bolg_а. The research has been carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University [88]. The authors also acknowledge the Plateforme Technologique de Calcul Intensif (P.T.C.I.; http://www.ptci.unamur.be), located at the University of Namur, which is part of the Consortium des Equipements de Calcul Intensif (C.E.C.I. supported by the F.R.S.-FNRS, Belgium; http://www.ceci-hpc.be).
Publisher Copyright:
© 2022 Elsevier B.V.
PY - 2023/1/15
Y1 - 2023/1/15
N2 - A climbing image nudged elastic band (cNEB) algorithm was applied on the basis of density functional theory (DFT) calculations of the rotational barriers of eight linear molecules (H
2, N
2, O
2, CO, CO
2, NO, N
2O, C
2H
2) adsorbed in NaY and NaCaY periodic zeolite models at the MeII cation sites (the Na or Ca metal cation in the SII site) located near the 6R windows. A specific approach is applied for molecules with positive quadrupole (H
2, C
2H
2) and small negative quadrupole (
3O
2) moments while applying cNEB. The obtained T-geometry relative to the cation is the most frequent case for H
2 adsorption in cationic form sieves and metalorganic frameworks (MOFs). The computed barriers for the T- and other linear (L) orientations are in good correlation with the quadrupole moments taken from literature irrespective of the dipole values (CO, NO, N
2O). In the case of NaY, the Al distribution per 6R sites is also discussed which allowed finding particular favorite adsorption sites. The calculated zero-point energies relative to the obtained rotational barriers regarding the H
2 - D
2 pair result in a qualitative agreement with the experimental isotopic difference in the H
2/D
2 adsorption heats in NaY which ultimately lead to the H
2/D
2 separation coefficient.
AB - A climbing image nudged elastic band (cNEB) algorithm was applied on the basis of density functional theory (DFT) calculations of the rotational barriers of eight linear molecules (H
2, N
2, O
2, CO, CO
2, NO, N
2O, C
2H
2) adsorbed in NaY and NaCaY periodic zeolite models at the MeII cation sites (the Na or Ca metal cation in the SII site) located near the 6R windows. A specific approach is applied for molecules with positive quadrupole (H
2, C
2H
2) and small negative quadrupole (
3O
2) moments while applying cNEB. The obtained T-geometry relative to the cation is the most frequent case for H
2 adsorption in cationic form sieves and metalorganic frameworks (MOFs). The computed barriers for the T- and other linear (L) orientations are in good correlation with the quadrupole moments taken from literature irrespective of the dipole values (CO, NO, N
2O). In the case of NaY, the Al distribution per 6R sites is also discussed which allowed finding particular favorite adsorption sites. The calculated zero-point energies relative to the obtained rotational barriers regarding the H
2 - D
2 pair result in a qualitative agreement with the experimental isotopic difference in the H
2/D
2 adsorption heats in NaY which ultimately lead to the H
2/D
2 separation coefficient.
UR - http://www.scopus.com/inward/record.url?scp=85141485710&partnerID=8YFLogxK
U2 - 10.1016/j.matchemphys.2022.126929
DO - 10.1016/j.matchemphys.2022.126929
M3 - Review article
SN - 0254-0584
VL - 294
JO - Materials Chemistry and Physics
JF - Materials Chemistry and Physics
M1 - 126929
ER -