Hydration of HAsO4-2: An ab initio QMCF MD Simulation

Anirban Bhattacharjee Theoretical Chemistry Division University of Innsbruck

Relevance

Arsenic removal techniques are normally followed by conversion of As(III) to As(V). In neutral aqueous medium AsO4-3 remains as HAsO4-3. Insight into the microstructure would be beneficial for desiging catalysts for removal process.

Experimental studies
Most of the experimental studies are aiming towards the removal technique, the behavior of the adsorped Arsenate species and their spectroscopic evaluation. However the informations retrieved from those studies concerning the hydration structures are. 1.As-O bondlength=1.67 respectively) and 1.74 (As-ON and As-OP

2. As-OP and AsON stretching frequencies ={680, 859}(ATRFTIR) ,{707 ,866}(Raman). 3. Internal distortion of tetrahedral gemometrey and bending of the protonated oxygen towards non protonated one. (OP ,ON stands for protonated and non prtonated arsenate oxygens.OW, HW would denote oxygens and hydrogens of water.)
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Simulation :
QMCF MD approach has been used to simulate HAsO4-2 in 999 water box at 298 K. QM core was set to 3.2 and QM layer 6.0. Smoothing was applied at the distance between 5.8 to 6.0 . Berendsen algorithm was used for thermostatisation and long range couloumbics were handled using reaction field. The equilibration was performed ove 5 ps simulation time, while 12 ps sampling time has been used to obtain the recorded trajectories (at 1 femtoseconds interval) which has been subjected to analysis.

Results and DIscussion

1.Radial Distributions 2.Intramolecular structural and spectral analysis 3.Coordination environment

RDFs -As-O

The first intramolecular peak shows a subtle splitting with peak positions 1.67 and 1.78 ( can be assigned to the As-ON and As-OP distances obtained from experiments, which are 1.67 and 1.74 respectively).

RDF-As-H

The first peak corresponds to the hydrogen atom bonded to one of the Arsenate oxygens. The mean distance obtained is 2.34 for the As-Hintra average distance

RDF( AS-O, As-H excluding intra molecular components)

As-OW rM1=3.85 rm1=4.85 CN1=11.81 As-HW rM1=2.95 rm1=3.75 CN1=11.27 Looking at the A-H distribution it can be concluded that apparently there is no second hydration shell.
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RDF :ON-HW, OP-HW

ON-HW rM1=1.66 rm1=2.56 CN1=2.5 OP-HW rM1=1.81 rm1=2.56 CN1=1.2 ON is far more calpable of forming H-Bonds with solvent water molecules.

RDF :HAs-OW

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Intramolecular properties:stretching freqency

the As-ON stretching frequency obtained from VACF and normal coordinate analysis is 855 cm-1(ATR-FTIR exp. 859cm-1) The As-OP stretching frequency obtained from VACF and normal coordinate analysis is 660 cm-1(ATR-FTIR exp. 680 cm-1) Both are in good agreement with the experimental results. Clearly reproduces the effect of protonation on As-O vibration.

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Angular distributions

ON-As-ON angle distribution shows a maxima at 113 while ON-As-OP angle shows maxima around 104-105. Which clearly depicts the bending of protonated oxygen towards the non protonated one, as it has been reported by the experimental studies.

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Distance plots :

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Coordination environment (I)

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Coordination environment(II)

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Scheme used for probing H-Bonds

The pure geometrical definition of the H bond has been used. Distance cutoffs has been chosen as the first minima in the corresponding radial distributions. The angle cutoff has been selected as 35 as that has been used for probing H-Bonds in phosphate derivatives.

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H-Bonding with water

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A snapshot depicting three hydrogen bonds formed by ON site.

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Conclusions

The present work has provided a direct insight into the hydration of the system, along with the successful reproduction of the experimentally available informations. The hydration layer is not uniform and the irregularity arises because of the protonation of one oxygen. The nomral scheme of probing mean residence time based on spherical selections will not provide adequate description of the dynamics as there are two different domains of hydration with varying hydrogen bond pattern. A direct calculation of hydrogen bond lifetimes at the different sites appears to be more significant description of the dynamics of the system.

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To be continued....................

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