Vibrational energies of some diatomic molecules for a modified and deformed potential

A molecular potential model is proposed and the solutions of the radial Schrӧdinger equation in the presence of the proposed potential is obtained. The energy equation and its corresponding radial wave function are calculated using the powerful parametric Nikiforov–Uvarov method. The energies of cesium dimer for different quantum states were numerically obtained for both negative and positive values of the deformed and adjustable parameters. The results for sodium dimer and lithium dimer were calculated numerically using their respective spectroscopic parameters. The calculated values for the three molecules are in excellent agreement with the observed values. Finally, we calculated different expectation values and examined the effects of the deformed and adjustable parameters on the expectation values.

Vibrational energies of some diatomic molecules for a modified and deformed potential

A molecular potential model is proposed and the solutions of the radial Schrӧdinger equation in the presence of the proposed potential is obtained. The energy equation and its corresponding radial wave function are calculated using the powerful parametric Nikiforov-Uvarov method. The energies of cesium dimer for different quantum states were numerically obtained for both negative and positive values of the deformed and adjustable parameters. The results for sodium dimer and lithium dimer were calculated numerically using their respective spectroscopic parameters. The calculated values for the three molecules are in excellent agreement with the observed values. Finally, we calculated different expectation values and examined the effects of the deformed and adjustable parameters on the expectation values.

Ro-vibrational energies of cesium dimer and lithium dimer with molecular attractive potential

An approximate solution of the Schrӧdinger equation for a molecular attractive potential was obtained using the parametric Nikiforov–Uvarov method. The energy equation and the corresponding radial wave functions were calculated. The effects of the potential parameters on the energy eigenvalues were examined. The thermal properties under the molecular attractive potential were calculated and the behaviour of the thermal properties with the maximum quantum state (λ) and the temperature parameter (β) respectively, were studied. Using the molecular spectroscopic parameters, the Rydberg–Klein–Rees (RKR) of cesium dimer and lithium dimer were both obtained and compared with the experimental values. The RKR values of both cesium dimer and lithium dimer calculated aligned with the observed values. The deviation and average deviation of the RKR for each molecule were also calculated.

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>