Effect of Pulsing Configuration and Magnetic Balance Degree on Mechanical Properties of CrN Coatings Deposited by Bipolar-HiPIMS onto Floating Substrate

Despite its great potential for thin films deposition and technological applications, the HiPIMS technology has its own limitations including the control of ion energy and flux towards the substrate when coping with the deposition of electrical insulating films and/or the deposition onto insulating/electrically grounded substrates. The bipolar-HiPIMS has been recently developed as a strategy to accelerate the plasma ions towards a growing film maintained at ground potential. In this work, the benefits of bipolar-HiPIMS deposition onto floating or nonconductive substrates are explored. The effect of bipolar-HIPIMS pulsing configuration, magnetic balance-unbalance degree, and substrate’s condition on plasma characteristics, microstructure evolution, and mechanical properties of CrN coatings was investigated. During the deposition with a balanced magnetron configuration, a significant ion bombardment effect was detected when short negative pulses and relative long positive pulses were used. XRD analysis and AFM observations revealed significant microstructural changes by increasing the positive pulse duration, which results in an increase in hardness from 7.3 to 16.2 GPa, during deposition on grounded substrates, and from 4.9 to 9.4 GPa during the deposition on floating substrates. The discrepancies between the hardness values of the films deposited on floating substrates and those of the films deposited on grounded substrates become smaller/larger when a type I/type II unbalanced magnetron configuration is used. Their hardness ratio was found to be 0.887, in the first case, and 0.393, in the second one. Advanced application-tailored coatings can be deposited onto floating substrates by using the bipolar-HiPIMS technology if short negative pulses, relative long positive pulses together with type I unbalanced magnetron are concomitantly used.

Quasi-Relativistic Calculation of EPR g-Tensors with Derivatives of the Decoupling Transformation, Gauge-Including Atomic Orbitals, and Magnetic Balance

We present an exact two-component (X2C) ansatz for the EPR g-tensor using gauge-including atomic orbitals (GIAOs) and a magnetically balanced basis set expansion. In contrast to previous X2C and "fully" relativistic ansätze for the g-tensor, this implementation results in a gauge-origin invariant formalism. Furthermore, the derivatives of the relativistic decoupling matrix are considered to form the complete analytical derivative of the X2C Hamiltonian. To reduce the associated computational costs, we apply the diagonal local approximation to the unitary decoupling transformation (DLU) and the (multipole-accelerated) resolution of the identity approximation. The X2C ansatz is compared to Douglas-Kroll-Hess theory and the zeroth-order regular approximation for 11 diatomic molecules. The impact of the relativistic Hamiltonian, the basis set, and the density functional approximation is subsequently assessed for a set of 17 transition-metal complexes to complement our previous work on the hyperfine coupling constant [DOI: 10.33774/chemrxiv-2021-wnz1v-v2]. In total, 24 basis sets and 22 density functional approximations are considered. The quasi-relativistic X2C and DLU-X2C Hamiltonians accurately reproduce the results of the parent "fully" relativistic four-component theory when accounting for two-electron picture-change effects with the modified screened nuclear spin-orbit approximation in the respective one-electron integrals and integral derivatives. Generally, the uncontracted Dyall and segmented-contracted Karlsruhe x2c-type basis sets perform well when compared to large even-tempered basis sets. Moreover, (range-separated) hybrid density functional approximations are needed to match the experimental findings. Here, hybrids based on the meta -generalized gradient approximation are not an a priori improvement. Compared to the other computational parameters, the impact of the GIAOs and the magnetic balance on the actual results in standard calculations is less pronounced. Routine calculations of large molecules are possible with widely available and comparably low- cost hardware as demonstrated for [Pt(C6Cl5)4]− with 3360 basis functions and three spin-(1/2) La(II) and Lu(II) compounds. Both approaches based on a common gauge origin and GIAOs using triple- ζ basis sets lead to a good agreement with the experimental findings. The best agreement is found with hybrid functionals such as PBE0 and ωB97X-D.

Quantitative prediction and interpretation of spin energy gaps in polyradicals: the virtual magnetic balance

Open-shell organic molecules possessing more than two unpaired electrons and sufficient stability at room temperature are very unusual, but some of them were recently synthesized and promise a number of fascinating applications.