Does Uranium-superoxide (UIII-O2) have

capability for the detoxification of industrial

wastes? Arvind Kumar Dwivedi#1, Jitendra kumar*2, Manjesh Kumar*3, Deep Kumar#4

1Department of Physics, M. L. K. (P.G.) college Balrampur U.P. India.

2Department of Physics , Babasaheb Bhimrao Ambedkar Univesity, Lucknow, India

3Department of Mathematics , Babasaheb Bhimrao Ambedkar Univesity, Lucknow, India

4Department of Basic Science, Babasaheb Bhimrao Ambedkar Univesity, Lucknow, India

Abstract: Theoretical studies on the molecular structure, the nature of superoxide complexes of uranium (UIII-O2)

bonding,vibrational frequencies, and intensities were performed by employing different DFT methods, including hybrid

(MO6, and B3LYP) and long-range-corrected hybrid density functionals (B3LYP). Various effective core potentials

(ECP) and basis sets have been used. In the prediction of the molecular structure of Uranium-superoxide (UIII-O2), the

best results have been obtained by MO6 and B3LYP density functionals, while the least accurate is B3LYP. The use of the

LanL2TZ(f) ECP/basis set for Uranium-superoxide, in conjunction with all tested DFT methods, improves the calculated

geometry of the title complex. Superoxide complexes of uranium (UIII-O2) are surprisingly rare but have attracted interest

in nonradioactive industrial applications. There is a current interest in the chemistry of uranium with atmospheric

components like carbon, nitrogen and oxygen in relation with the development of gas-phase separations involving atomic

uranium.

Keywords: DFT,B3LYP, molecular structure, enzyme

I. Introduction

Nature utilizes molecular oxygen for many important biotransformations, including biocatalysis,

biodegradation and biosynthesis. High-valent metal–oxo complexes are ubiquitous species used in nature

and in the laboratory for the purpose of oxygenation of organic compounds. While iron is the most

common metal in these species, there are also complexes with manganese–oxo, copper–oxo, and other

moieties. The importance of metal–oxo species cannot be overstated, and the interest in their reaction

mechanisms matches this distinction. The role of high-valent iron-oxo complexes in oxidative

transformations of C-H bonds is now commonly recognized.[1-5] Cytochrome P450 (P450) enzymes that

are thought to make use of such a species are powerful oxidants capable of hydroxylating alkanes with C-

H bond strengths ranging from very strong to very weak.[2,6] Many synthetic analogues of P450 and of

nonheme enzymes having high-valent metal-oxo complexes have been made and demonstrated to perform

C-H hydroxylation reactions.[7] Metalsuperoxo species have attracted much attention recently, since the

intermediates have been proposed as active oxidants in C–H bond activation reactions by metalloenzymes

and their biomimetic counterparts.

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Figure 1: O–O Bond Activation in Iron-Based Complexes and Enzymes

Uranium by itself has relatively few industrial uses and is commonly removed from raw materials such as

fertilizers containing phosphate as a waste product during processing, or because of environmental

concerns where it is often removed with other heavy metals such as cadmium. Uranium is also

occasionally used as a catalyst in certain specialized chemical reactions and in photographic films. In the

recent past the low dimensional material has become of great interest in the research field of nanoscience.

[8,9]

Although terminal superoxide complexes of uranium (UIII-O2) are surprisingly rare but have attracted

interest in nonradioactive industrial applications. There is a current interest in the chemistry of uranium

with atmospheric components like carbon, nitrogen and oxygen in relation with the development of gas-

phase separations involving atomic uranium.[10-14]

II. Methods

For optimization of Uranium-superoxide (UIII-O2) and to calculate their ground and excited state properties, we

have used density functional theory. Structural optimizations (i.e. the geometrical parameters) have been done with

no constraints imposed on the Uranium-superoxide (UIII-O2) structures during the optimization. For geometry

optimization and vibrational analysis, B3LYP level of DFT method, Beck’s three parameters with correlation

function (Lee-Yang-Parr), and relativistic effective core potential with double zeta basis set, LANL2DZ as

implemented in Gaussian 09 programme suit [15] are used.

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III. Results and Discussion

The optimized molecular geometry and the numbering of atoms of Uranium-superoxide (UIII-O2) are

shown in Figure 2 presents optimized geometry for singlet, triplet and quintet. It is clear from figure 1 that UIII-O2

bond distance is comparable to other metal-O2 of heme and non-heme type system. Table 1 presents relative spin

splitting and results suggest that quintet is ground state similar to other metal-O2 of heme and non-heme type system

and singlet and triplet spin state are much higher.

Figure 2: Optimized Geometry of UIII-O2. All bond lengths are given in angstroms and values in square bracket are for

quintet, in parentheses are for triplet and rest are for singlet spin states, respectively.

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Table 1: Electronic energies, free energies are in Hartree and relative energies are in kcal/mol.

a. B3LYP

Multip E E+ZPC G E E+ZPC G

M1 -26183.941593 -26183.815405 -26183.864791 74.29 74.89 77.57

M3 -26183.986170 -26183.860140 -26183.910060 46.32 46.82 49.17

M5 -26184.059990 -26183.934760 -26183.988420 0.00 0.00 0.00

b. MO6//B3LYP

Multip E E+ZPC E E+ZPC

M1 -26183.167710 -26183.041530 73.19 73.79

M3 -26183.219110 -26183.093080 40.94 41.44

M5 -26183.284360 -26183.159130 0.00 0.00

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Figure 3: Molecular orbital for UIII-O2 for singlet spin state. The relative energies are in Hartree.

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Figure 4: Molecular orbital for UIII-O2 for triplet spin state. The relative energies are in Hartree.

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Figure 5: Molecular orbital for UIII-O2 for quintet spin state. The relative energies are in Hartree.

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Figure 3-5 presents molecular orbitals and their relative energies with respect to HOMO and LUMO. Table 2

present electron affinity and OH bond dissociate energies (BDEOH).

Table 2: Electronic affinity (EA) and ionization potential (IP) in kcal/mol.

EA EA+ZPC BDEOH BDEOH+ZPC

B3LYP -187.29 -186.68 B3LYP -57.87 -50.02

MO6 -196.67 -196.05 MO6 -62.81 -54.96

The computed EA and BDEOH for UIII-O2 are comparable with that of the other metal-O2.15 which suggest that UIII-

O2 can be act as potent oxidant for CH bond activation to convert water insoluble to soluble product.

IV. References

[1] M. Sono, M. P. Roach, E. D. Coulter and J. H. Dawson, Heme-Containing Oxygenases" Chem. ReV. vol.96, pp. 2841-2888, Nov. 1996.

[2] J. T. Groves, in Cytochrome P450: Structure, Mechanism, and Biochemistry, 3rd ed.; Ortiz de Montellano, P. R., Ed.; Kluwer

Academic/Plenum: New York, 2005.

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catalytic pathway of cytochrome p450cam at atomic resolution", Science, vol. 287, pp.1615-1622, Mar.2000.

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[6] D. Kumar, S. P. de Visser, P.K. Sharma, H. Hirao, and S. Shaik," Sulfoxidation Mechanisms Catalyzed by Cytochrome P450 and

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[7] J. T. Groves, " High-valent iron in chemical and biological oxidations" J. inorg. Biol. Chem., vol.100, pp.434-447,Apr.2006.

[8] D. Kumar, A.Kumar, J. Kumar, and D. Kumar, Advanced Science,Engineering and Medicine," Strucral stability and electronic property of

(GanNn)m micro cluster by using AB initio and tight Binding study” Adv. sci.eng. and med., vol.10,pp.1-5,Dec.2018

[9] D. Kumar, A.Trivedi and D. Kumar "Quantum mechanical study of GaxAsx fullerene type Micro-Clusters for X=10, 13, 15, 18, 20, 25 and 30

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[10] B. O. Roos, R. Lindh, P.A. Malmqvist, V. Veryazov, P.O. Widmark," New Relativistic ANO Basis Sets for Transition Metal Atoms"

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[13] A. Aguado, L. Bernasconi, S. Jahn and P. A. Madden," Multipoles and interaction potentials in ionic materials from planewave-DFT calculations"

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[1

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