Posted on04/01/2019byPavlin Mitev|Comments Off on Fifty Shades of Water: Benchmarking DFT Functionals against Experimental Data for Ionic Crystalline Hydrates
Authors: Getachew Kebede, Peter Broqvist, Anders Eriksson, and Kersti Hermansson
We propose that crystalline ionic hydrates constitute a valuable resource for benchmarking theoretical methods for aqueous ionic systems. Many such structures are known from the experimental literature, and they contain a large variety of water–water and ion–water structural motifs. Here we have collected a data set (CRYSTALWATER50) of 50 structurally unique “in-crystal” water molecules, involved in close to 100 nonequivalent O–H···O hydrogen bonds. A dozen well-known DFT functionals were benchmarked with respect to their ability to describe these experimental structures and their OH vibrational frequencies. We find that the PBE, RPBE-D3, and optPBE-vdW methods give the best H-bond distances and that anharmonic OH frequencies generated from B3LYP//optPBE-vdW energy scans outperform the other methods, i.e., here we performed B3LYP energy scans along the OH stretching coordinate while the rest of the structure was kept fixed at the optPBE-vdW-optimized positions
Posted on12/01/2016byPavlin Mitev|Comments Off on H-bond and electric field correlations for water in highly hydrated crystals
Authors: Anik Sen, Pavlin D. Mitev, Anders Eriksson, and Kersti Hermansson
We present periodic plane-wave density functional theory (DFT) Perdew–
Burke–Ernzerhof (PBE-D2) calculations for four highly hydrated crystals, Na2CO3·10H2O, MgSO4·7H2O, MgSO4·11H2O, and Al(NO3)3·9H2O, containing 37 structurally unique water molecules and 74 unique hydrogen bonds. The calculated R(H···O) distances lie in the range 1.60–2.05 Å, the anharmonic OH frequencies in the range 2570–3425 cm−1, and the water dipole moments lie in the range 2.9–4.3 Debye, as calculated from the Wannier function centers and the nuclei. We present the following findings. (i) Our optimized intramolecular r(OH) distances are always larger than the gas-phase value and thus more accurate than those derived from neutron diffraction experiments; (ii) The local in situ electric field over the molecule, calculated from the positions of the nuclei and the Wannier centers in the surrounding crystal, appears to be a good descriptor of the pertturbation from the water molecule’s surroundings as the internal molecular properties (re, ν, μ) are found to correlate well with the crystal-generated electric field; (iii) We have added DFT-calculated data points to the well-known experimental ‘OH frequency versus R(H···O)’ correlation curve in a region where the experimental data points are scarce; (iv) For all 37 water molecules, the Wannier centers located in the lone-pair region, and those located in the OH bonds, displace about equally much due to the polarizing environment. Finally, we propose that our resulting ‘OH frequency versus Wannier-type electric field’ correlation curve may constitute a useful tool for predicting OH vibrational frequencies from snapshots from PBE-D2-based ab initio molecular dynamics simulations of water-containing systems.
International Journal of Quantum Chemistry, 116, ( 2016), 67-80 DOI: 10.1002/qua.25022
Posted on25/03/2015byPavlin Mitev|Comments Off on Vibrational models for a crystal with 36 water molecules in the unit cell: IR spectra from experiment and calculation
Authors: Pavlin D. Mitev, Anders Eriksson, Jean-François Boily and Kersti Hermansson
We present experimental and calculated IR spectra of the water molecules in crystalline aluminium nitrate nonahydrate and a method to generate a realistic and well resolved isotope-isolated spectrum from periodic DFT calculations. Our sample crystal contains 18 structurally different OH groups and is a perfect benchmark compound to validate vibrational models and the structure–property relationship of bound water molecules. FTIR spectra (ATR technique) were recorded for the Al(NO3)3·9H2O crystal at 138 and 298 K, and due to a multitude of OH contributions and couplings, they are naturally poorly resolved and yield a broad OH band in the range 3500 to 2700 cm−1 at both temperatures. Isotope-isolated IR spectra have the clear advantage over non-deuterated spectra that they are better resolved and easier to interpret – here we have extended the experimental study by simulating the isotope-isolated IR spectrum, using PBE-D2 and auxiliary B3LYP calculations and an anharmonic OH vibrational model. We find excellent agreement between the shapes and frequency ranges of the experimental and calculated OH spectral bands. We make use of four different vibrational models: (i) a harmonic lattice-dynamical model for the isotope-isolated crystal with 1 H among 71 D, (ii) a harmonic lattice-dynamical model for the normal undeuterated crystal involving all the vibrational couplings, (iii) a harmonic 1-dimensional uncoupled OH vibrational model, and (iv) the anharmonic variant of the previous model, which yields the final spectrum. We also use the individual frequencies, resolved by the calculations, to quantify new or extended relationships involving OH frequencies versus local electric fields and H-bond distances. We explore the correlation between OH frequency and molecular dipole moment for bound water molecules.
Posted on10/04/2014byPavlin Mitev|Comments Off on Large polarization but small electron transfer for water around Al3+ in a highly hydrated crystal
Authors: Pavlin D. Mitev, Imre Bakó, Anders Eriksson and Kersti Hermansson
Precise molecular-level information on the water molecule is precious, since it affects our interpretation of the role of water in a range of important applications of aqueous media. Here we propose that electronic structure calculations for highly hydrated crystals yield such information. Properties of nine structurally different water molecules (19 independent OO hydrogen bonds) in the Al(NO3)3·9H2O crystal have been calculated from DFT calculations. We combine the advantage of studying different water environments using one and the same compound and method (instead of comparing a set of independent experiments, each with its own set of errors) with the advantage of knowing the exact atomic positions, and the advantage of calculating properties that are difficult to extract from experiment. We find very large Wannier dipole moments for H2O molecules surrounding the cations: 4.0–4.3 D (compared to our calculated value of 1.83 D in the gas phase). These are induced by the ions and the H-bonds, while other water interactions and the relaxation of the internal water geometry in fact decrease the dipole moments. We find a good correlation between the water dipole moment and the OO distances, and an even better (non-linear) correlation with the average electric field over the molecule. Literature simulation data for ionic aqueous solutions fit quite well with our crystalline ‘dipole moment vs. OO distance’ curve. The progression of the water and cation charges from ‘small clusters ⇒ large clusters ⇒ the crystal’ helps explain why the net charges on all the water molecules are so small in the crystal.