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A ROBUST HYBRID STATISTICAL PHYSICS QUANTUM CHEMICAL APPROACH TO MAGNETIC PROPERTIES OF

COMPLEX AQUEOUS ALUMINUM(III) SPECIES: IMPLEMENTATION ON HPC ENVIRONMENT

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Bojana Koteska, MSc1; Anastas Mishev, PhD1; Ljupco Pejov, PhD2

1FSCE, UKIM, Skopje, 2FNSM, UKIM, Skopje

Introduction

Results and Discussion - The structure of the liquid in the neighborhood of Al3+ ions

It has been well recognized in physical and engineering sciences that a

thorough understanding of the properties of ionic/molecular species in
condensed phases is crucial for better understanding and realistic modeling of
processes taking place in biochemical, geochemical and other environments.
However, development of reliable and robust theoretical models that
explicitly include the influence of condensed phase environment, in particular
its dynamical characteristics, appears to be far from a trivial task.

Due to the strong electrostatic interaction between the central Al3+ ions and the hydroxide ions, the anionic species reside in close vicinity of the cation. This
can be clearly seen from the AlOOH- radial distribution function shown in the Fig. 1.
The sharp peak in the mentioned RDF end up at r < 1.75 , in line with the previous discussion. The AlOwater RDF is, on the other hand, shown below (Fig 2).
The corresponding AlOwater RDF computed from an equilibrated Monte Carlo run for aqueous Al3+ ionic solution is shown in Fig. 3 below.
2.50

30000

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One side of the problem is to find a fundamentally correct way to include the
condensed-phase environment in the model, while the other side is a purely
computational aspect of the problem. Related to the later problem is the
need for large computational resources, development of new efficient
algorithm for data analysis as well as the effective use of computational
resources (which is again, a programming-related problem).

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2.00

16.00
14.00

20000
1.50

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15000
1.00

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10000

6.00

Aims of the Current Study

In the present study, we address a particularly relevant problem
computation of magnetic response properties of aqueous aluminum(III)
complex ionic species - the Al(H2O)63+ and Al(OH)4- ions.

5000
2.00

0.00

0.00

0
0

We develop and implement a hybrid statistical physics quantum mechanical

approach to compute the 27Al NMR shielding tensor and the corresponding
isotropic shielding. To account for the fluctuating character of the condensedphase environment, we first carry out a statistical physics Monte Carlo
simulation of Al(H2O)63+ and Al(OH)4- aqueous solutions, followed by
subsequent quantum mechanical computations of magnetic response
properties of charge-embedded clusters with varying size and complexity.

4.00

0.50

10

15

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Figure 1. Radial Distribution Function.

The distribution histograms for the isotropic shielding constant values computed for the aqueous Al(III) ion from MC simulations of Al3+ + 4 OH- + water
system, including explicitly both the first and the second hydration shell around the Al3+ ions (with the CSGT method) is shown in Fig 4. Figure 5, on the other
hand, shows the corresponding histogram derived from the MC simulations of aqueous Al(H2O)63+ species.
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CSGT

<iso> = 475.2 ppm

<iso> = 557.3 ppm

Conclusion

Computational Strategy

The average isotropic shielding of the

Al(OH)4- species, computed with respect
to Al(H2O)63+ species (i.e. as a difference
between average isotropic shielding
constants) is thus 82.1 ppm.

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Occurrence

Occurrence

40

10

The corresponding experimental value is

80.0 ppm. The relative error of the
computations carried out by our hybrid
robust methodology is thus as small as
2.6 %.

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0
-2000

-1000

1000

2000

3000

iso / ppm

0
540

550

iso / ppm

560

570

Figure 5. Distribution histogram Al(H2O)63+

Figure 4. Distribution Histogram Al(OH)4-

Contact
Bojana Koteska
Faculty of Computer Science and Engineering, UKIM, Skopje, Macedonia
Email: bojana.koteska@finki.ukim.mk
Website: http://finki.ukim.mk
Phone: 0038975399556

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Results and Discussion - Magnetic Shielding

CSGT

Subsequently, the MC trajectories are analyzed by time-series analytic

methods (implementing the energy autocorrelation functions) so that out of a
very large overall number of MC configurations that have been generated,
only 100 representative ones are picked up, with negligible mutual statistical
interdependence. NMR shielding tensors are subsequently computed for such
chosen configurations at B3LYP/6-311++G(3df, 3pd) level of theory, using
various approaches to include the environment of the central Al ion.

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Figure 3. AlOwater RDF from Monte Carlo Run.

Figure 2. AlOwater RDF.

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In the developed approach, first, Metropolis Monte Carlo simulation (NPT

ensemble) of water solution containing Al3+ and 3000 water molecules, or
Al3+, 4 OH- ions, and 3000 water molecules in a cubic box, employing periodic
boundary conditions is carried out.

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r/

r/

r/

References
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7.

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Ditchfield, R.: Self-consistent perturbation theory of diamagnetism. Molecular Physics 27(4), 789807 (1974)
Keith, T., Bader, R.: Calculation of magnetic response properties using atoms in molecules. Chemical Physics Letters 194(12), 18 (1992)
Keith, T.A., Bader, R.F.: Calculation of magnetic response properties using a continuous set of gauge transformations. Chemical Physics Letters 210(13), 223231 (1993)
Tossell, J.: Nuclear magnetic shieldings and molecular structure. NATO ASI series: Mathematical and Physical Sciences. Kluwer Academic Publishers (1993)
Wolinski, K., Hinton, J.F., Pulay, P.: Efficient implementation of the gauge independent atomic orbital method for nmr chemical shift calculations. Journal of the American Chemical Society 112(23), 82518260 (1990)