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Density functional theoretical assessment of titanium metal for adsorption of hydrogen, deuterium and tritium isotopes

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Abstract

Titanium, a high-temperature tolerance metal, is preferred as neutron targets due to high hydrogen storage capacity. Therefore, there is a need to understand the interaction and dynamical behaviours of hydrogen isotopes with Ti which is investigated by means of linear combination of atomic orbitals and projector augmented wave (PAW) potential within the density functional theoretical framework. The hydrogen isotope is studied by incorporating zero point energy and the harmonic transition state theory (HTST) was used to determine the rate constant. The values of surface adsorption energy of hydrogen isotopes were predicted to follow the trend: Ead(H2) > Ead(D2) > Ead(T2). The activation energy barrier from top to bridge and top to hollow sites was negative for H atom indicating barrier less diffusion. The computed total density of states and partial density of states confirmed that the hollow site offers the most stable site for H atom adsorption than that by bridge and top sites. The calculated barrier height for dissociation was 0.4 eV at surface coverage of θH > 0.5 ML, whereas the barrier height for recombination was found to be much higher than that of dissociation. The calculated dissociation rate constant using HTST was found to be quite fast, whereas the rate constant for recombination was determined to be very slow as expected. The ZPE corrected activation heights for bulk diffusion in Ti from one Td void to nearby Td void for H, D and T were computed to be 0.118, 0.126 and 0.129 eV, respectively, at the PAW level. The calculated diffusivity establishes that the lighter H atom migrates faster than that of heavier D and T atoms. The classical barrier height was observed to be reduced after quantum correction.

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Acknowledgements

The computer division of BARC is acknowledged for making ANUPAM Supercomputing facility available to us. Dr. S. Mukhopadhyay, Head, ChED and Shri K.T. Shenoy, Director, ChEG are gratefully acknowledged for continuous support and encouragement.

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  1. Chemical Engineering Division, Bhabha Atomic Research Centre, Mumbai, Maharashtra, 400085, India

    Anil Boda & Sk. Musharaf Ali

  2. Computer Division, Bhabha Atomic Research Centre, Mumbai, Maharashtra, 400085, India

    Nirbhay Chandorkar

  3. Homi Bhabha National Institute, Mumbai, Maharashtra, 400094, India

    Anil Boda & Sk. Musharaf Ali

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Sk. Musharaf Ali designed the research; Anil Boda performed the simulations and data analysis and initial manuscript preparation; Sk. Musharaf Ali edited the final manuscript. Nirbhay Chandorkar contributed code implementation in supercomputing facility; All authors contributed to editing the manuscript, and approve of the content in its current form.

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Boda, A., Chandorkar, N. & Ali, S.M. Density functional theoretical assessment of titanium metal for adsorption of hydrogen, deuterium and tritium isotopes. Theor Chem Acc 142, 46 (2023). https://doi.org/10.1007/s00214-023-02988-9

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