Geometric and electronic structure analysis of calcium water complexes with one and two solvation shells

2020 ◽  
Vol 22 (39) ◽  
pp. 22426-22435 ◽  
Author(s):  
Isuru R. Ariyarathna ◽  
Evangelos Miliordos
Keyword(s):  
Electronic Structure ◽  
Structure Analysis ◽  
Electronic States ◽  
Excited Electronic States ◽  
Valence Electrons ◽  
The Stability

The stability of calcium water complexes is investigated quantum mechanically. Ground and excited electronic states are studied for hexa-, octa-, and octakaideca-coordinated complexes, where calcium valence electrons move to outer diffuse orbitals.

Ground and Excited Electronic Structure Analysis of XM4 (X = N, P and M = Li, Na) and their Anions

2021 ◽  
Author(s):  
Isuru R Ariyarathna
Keyword(s):  
Electronic Structure ◽  
Ab Initio ◽  
Structure Analysis ◽  
Electronic States ◽  
Coupled Cluster ◽  
Ab Initio Methods ◽  
Excited Electronic States ◽  
Electron Propagator ◽  
High Level

High-level coupled-cluster, electron propagator, and multi-reference ab initio methods are employed to study ground and excited electronic states of XM4 (X = N, P and M = Li, Na) series....

Transition-metal solvated-electron precursors: diffuse and 3d electrons in V(NH3)0,±6

2019 ◽  
Vol 21 (13) ◽  
pp. 7090-7097 ◽  
Author(s):  
Nuno M. S. Almeida ◽  
Filip Pawłowski ◽  
Joseph Vincent Ortiz ◽  
Evangelos Miliordos
Keyword(s):  
Electronic Structure ◽  
Transition Metal ◽  
Ab Initio ◽  
Electronic States ◽  
Electronic Structure Theory ◽  
Structure Theory ◽  
Solvated Electron ◽  
Excited Electronic States

Ground and excited electronic states of V(NH3)0,±6 complexes, investigated with ab initio electronic structure theory, consist of a V(NH3)62+ core with up to three electrons distributed over its periphery.

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

2019 ◽  
Author(s):  
Tatiana Woller ◽  
Ambar Banerjee ◽  
Nitai Sylvetsky ◽  
Xavier Deraet ◽  
Frank De Proft ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Basis Set ◽  
Dft Methods ◽  
Molecular Switching ◽  
Wide Range ◽  
Electronic Structure Methods ◽  
Explicitly Correlated ◽  
Relative Errors ◽  
The Stability ◽  
Basis Set Expansion

<p>Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. Taking into account its size and huge conformational flexibility, DFT remains the workhorse for modeling such extended macrocycles. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, p···p stacking, steric effects, ring strain and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wavefunction methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a pronouncedly stronger degree of static correlation than the Hückel and figure-eight structures, and as a result the relative energies of singly-twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between MP2/cc-pVDZ and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol<sup>-1</sup> with the CCSD(T) relative energies. Regarding DFT methods, only M06-2X provides relative errors close to chemical accuracy with a RMSD of 1.2 kcal mol<sup>-1</sup>. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended p-systems, the errors drop down to 2 kcal mol<sup>-1</sup> for the revised revDSD-PBEP86-NL, again showing that same-spin MP2-like correlation has a detrimental impact on performance like the SOS-MP2 results. </p>

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