Monte-Carlo Simulations of Spin-Crossover Phenomena Based on a Vibronic Ising-like Model with Realistic Parameters

Materials with spin-crossover (SCO) properties hold great potentials in information storage and therefore have received a lot of concerns in the recent decades. The hysteresis phenomena accompanying SCO is attributed to the intermolecular cooperativity whose underlying mechanism may have a vibronic origin. In this work, a new vibronic Ising-like model in which the elastic coupling between SCO centers is included by considering harmonic stretching and bending (SAB) interactions is proposed and solved by Monte Carlo simulations. The key parameters in the new model, $k_1$ and $k_2$, corresponding to the elastic constant of the stretching and bending mode, respectively, can be directly related to the macroscopic bulk and shear modulus of the material in study, which can be readily estimated either based on experimental measurements or first-principles calculations. The convergence issue in the MC simulations of the thermal hysteresis has been carefully checked, and it was found that the stable hysteresis loop can be more readily obtained when using the SAB model compared to that using the Wajnflasz-Pick model. Using realistic parameters estimated based on first-principles calculations of a specific polymeric coordination SCO compound, [Fe(pz)Pt(CN)$_4$]$\cdot$2H$_2$O, temperature-induced hysteresis and pressure effects on SCO phenomena are simulated successfully.Comment: 8 pages, 8 figure

CO Adsorption on the Surface of MgO from Periodic Coupled-Cluster Theory with Local Natural Orbitals: Adding to the Consensus

Accurate determination of the adsorption energy of CO on the MgO (001) surface has been a challenge for both computations and experiments over the past three decades. A recent computational study by Shi and co-workers (10.26434/chemrxiv-2023-h4czl) reported good agreement within $11$ meV ($1$ kJ/mol) between two popular theoretical methods: coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] and diffusion Monte Carlo. In this short note, we report results on the same problem from periodic Gaussian-based MP2, CCSD, and CCSD(T), with the latter two performed using a recently developed extension of the local natural orbital (LNO) approximation to problems with periodic boundary conditions. Our final periodic LNO-CCSD(T) adsorption energy ($-198 \pm 11$ meV) is in quantitative agreement with the embedded cluster-based LNO-CCSD(T) result ($-199 \pm 11$ meV) by Shi and co-workers. The computational cost of our periodic LNO-CCSD(T) calculations is comparable to that of the embedded cluster-based LNO-CCSD(T) and is 10 times less expensive than the plane-wave-based periodic canonical CCSD(T) or 50 times less expensive than the DMC calculations reported by Shi and co-workers. Our findings highlight the accuracy and computational efficiency of the periodic LNO-based approach for the simulation of surface chemistry with correlated wavefunction methods.Comment: 5 pages, 4 figures, 3 table

Ab initio surface chemistry with chemical accuracy

First-principles calculations are a cornerstone of modern surface science and heterogeneous catalysis. However, accurate reaction energies and barrier heights are frequently inaccessible due to the approximations demanded by the large number of atoms. Here we show that these approximations can be systematically eliminated to solve the many-electron Schr\"odinger equation for molecules on surfaces with chemical accuracy, commonly defined as 1 kcal/mol. As a demonstration, we study water on the surface of $\mathrm{Al}_2\mathrm{O}_3$ and $\mathrm{TiO}_2$, two prototypical and industrially important metal oxides for which we obtain converged energies at the level of coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], commonly known as the "gold-standard" in molecular quantum chemistry. We definitively resolve the energetics associated with water adsorption and dissociation, enabling us to address recent experiments and to analyze the errors of more commonly used approximate theories.Comment: 6 pages (w/o SI), 3 figure

The Effect of EMU Driver Operating Time on Professional Psychological Quality

Purpose: EMU driver operation time is an important part of the locomotive crew system. To ensure the safe, efficient and accurate operation of the EMU (Electric Multiple Unit), drivers not only need to have good physical and mental health but also must be able to work under the conditions of a scientific, reasonable and humanized organization.Design/methodology/approach: To effectively analyze the actual job of an EMU driver and to avoid impacting the normal work of the drivers, we selected some of the items from the professional mentality test project, which we had found had resulted in short test times and high test reliability and validity.Findings: With a single-driver continuous value multiplied by a time of less than two hours, there were no significant differences; multiplied by more than 4 hours, there was a significant difference in psychological quality; specifically, the multiplied career mental quality level decreased significantly. The EMU single continuous value multiplied by driving time driver should not be more than four hours to receive the full benefit. Originality/value: Based on the different operating times, this study compared the organization of different jobs in different situations. The negative impact of psychological load on EMU driver labor intensity varied

Integral-direct Hartree-Fock and M{\o}ller-Plesset Perturbation Theory for Periodic Systems with Density Fitting: Application to the Benzene Crystal

We present an algorithm and implementation of integral-direct, density-fitted Hartree-Fock (HF) and second-order M{\o}ller-Plesset perturbation theory (MP2) for periodic systems. The new code eliminates the formerly prohibitive storage requirements and allows us to study systems one order of magnitude larger than before at the periodic MP2 level. We demonstrate the significance of the development by studying the benzene crystal in both the thermodynamic limit and the complete basis set limit, for which we predict an MP2 cohesive energy of $-72.8$ kJ/mol, which is about $10$--$15$ kJ/mol larger in magnitude than all previously reported MP2 calculations. Compared to the best theoretical estimate from literature, several modified MP2 models approach chemical accuracy in the predicted cohesive energy of the benzene crystal and hence may be promising cost-effective choices for future applications on molecular crystals.Comment: 5 pages (w/o refs or SI), 3 figures, 1 tabl

β\beta-Ga2_2O3_3 Nano-membrane Negative Capacitance Field-effect Transistor with Steep Subthreshold Slope for Wide Bandgap Logic Applications

Steep-slope $\beta$-Ga$_2$O$_3$ nano-membrane negative capacitance field-effect transistors (NC-FETs) are demonstrated with ferroelectric hafnium zirconium oxide in gate dielectric stack. Subthreshold slope less than 60 mV/dec at room temperature is obtained for both forward and reverse gate voltage sweeps with a minimum value of 34.3 mV/dec at reverse gate voltage sweep and 53.1 mV/dec at forward gate voltage sweep at $V_{DS}$=0.5 V. Enhancement-mode operation with threshold voltage ~0.4 V is achieved by tuning the thickness of $\beta$-Ga$_2$O$_3$ membrane. Low hysteresis of less than 0.1 V is obtained. The steep-slope, low hysteresis and enhancement-mode $\beta$-Ga$_2$O$_3$ NC-FETs are promising as nFET candidate for future wide bandgap CMOS logic applications.Comment: 21 pages, 5 figure