A mass of oxygen vacancies are successfully introduced into TiO2 nanotube arrays using low-cost NaBH4 as a reductant in a liquid-phase environment. By controlling and adjusting the reduction time over the range of 0-24 h, the doping concentration of the oxygen vacancy is controllable and eventually reaches saturation. Meanwhile, the thermal stability of oxygen vacancies is also investigated, indicating that part of the oxygen vacancies remain stable up to 250 °C. In addition, this liquid-phase reduction strategy significantly lowers the requirements of instruments and cost. More interesting, reduced TiO2 nanotube arrays show drastically enhanced field emission performances including substantially decreased turn-on field from 25.01 to 2.65 V/μm, a high current density of 3.5 mA/cm(2) at 7.2 V/μm, and an excellent field emission stability and repeatability. These results are attributed to the oxygen vacancies obtained by reducing in NaBH4 solution, resulting in a reduced effective work function and an increased conductivity.

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The partially reduced TiO(2) nanotube arrays (TNAs) are prepared via an uncomplicated and low-cost liquid phase reduction strategy using NaBH(4) as the reducing agent. By controlling and adjusting the reduction temperatures from 30 to 90 °C, the reduction treatment can not only change their surface morphology but also introduce oxygen vacancies into them, resulting in an optimized morphology, elevated Fermi-level, reduced effective work function and improved conductivity of the TNAs. Meanwhile, the thermal and long-term stability of oxygen vacancy are also investigated, indicating that the oxygen vacancies retain long-term stability from room temperature up to 150 °C. More interesting, partially reduced TNAs show drastically enhanced field emission (FE) performances including substantially decreased turn-on field from 18.86 to 1.53 V μm(-1), a high current density of 4.00 mA cm(-2) at 4.52 V μm(-1), and an excellent FE stability and repeatability. These very promising results are attributed to the combination of the optimized morphology and introduced oxygen vacancies, which can increase FE sites, reduce effective work function and increase conductivity.

Main chain torsions of alanine dipeptide are parameterized into coupled 2-dimensional Fourier expansions based on quantum mechanical (QM) calculations at M06 2X/aug-cc-pvtz//HF/6-31G** level. Solvation effect is considered by employing polarizable continuum model. Utilization of the M06 2X functional leads to precise potential energy surface that is comparable to or even better than MP2 level, but with much less computational demand. Parameterization of the 2D expansions is against the full main chain torsion space instead of just a few low energy conformations. This procedure is similar to that for the development of AMBER03 force field, except unique weighting factor was assigned to all the grid points. To avoid inconsistency between quantum mechanical calculations and molecular modeling, the model peptide is further optimized at molecular mechanics level with main chain dihedral angles fixed before the calculation of the conformational energy on molecular mechanical level at each grid point, during which generalized Born model is employed. Difference in solvation models at quantum mechanics and molecular mechanics levels makes this parameterization procedure less straightforward. All force field parameters other than main chain torsions are taken from existing AMBER force field. With this new main chain torsion terms, we have studied the main chain dihedral distributions of ALA dipeptide and pentapeptide in aqueous solution. The results demonstrate that 2D main chain torsion is effective in delineating the energy variation associated with rotations along main chain dihedrals. This work is an implication for the necessity of more accurate description of main chain torsions in the future development of ab initio force field and it also raises a challenge to the development of quantum mechanical methods, especially the quantum mechanical solvation models.

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