Static Electron Correlation in Anharmonic Molecular Vibrations: A Hybrid TAO-DFT Study

Hanson‐Heine, Magnus W. D.

doi:10.1021/acs.jpca.2c05881

Cited by 8 publications

(7 citation statements)

References 93 publications

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“…In addition, several TAO-DFT-extensions [40][41][42][43][44] have been recently developed as well. Over the last few years, TAO-DFT has been employed to explore the electronic [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61], hydrogen storage [47,49,50], and spectroscopic [43,62,63] properties of gas-phase nanomolecules with MR character, outperforming KS-DFT with the widely used XC energy functionals. Moreover, a few recent studies [64][65][66][67] on the ground-state properties of electronic systems at absolute zero have been actually performed using an approximate TAO-DFT method (i.e., TAO-DFT without the θ-dependent energy functional [37]) at some fictitious temperature θ, which should not be confused with the Mermin-Kohn-Sham method (also called finite-temperature density functional theory (FT-DFT)) [23,68] at some finite electronic temperature due to their distinctly different physical meanings (e.g., see Refs.…”

Section: Of 18mentioning

confidence: 99%

TAO-DFT with the Polarizable Continuum Model

Seenithurai¹,

Chai²

2023

Preprint

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For the ground-state properties of gas-phase nanomolecules with multi-reference character, thermally-assisted-occupation density functional theory (TAO-DFT) has been recently found to outperform the widely used Kohn-Sham density functional theory, when the conventional exchange-correlation energy functionals are employed. Aiming to explore solvation effects on the ground-state properties of nanomolecules with multi-reference character at a minimal computational cost, we combine TAO-DFT with the polarizable continuum model (PCM). To show its usefulness, TAO-DFT-based PCM (TAO-PCM) is employed to study the electronic properties of linear acenes in three different solvents (toluene, chlorobenzene, and water). According to TAO-PCM, in the presence of these solvents, the smaller acenes should have nonradical nature, and the larger acenes should have increasing polyradical nature, showing remarkable similarities to the past findings in the gas phase.

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Section: Of 18mentioning

confidence: 99%

TAO-DFT with the Polarizable Continuum Model

Seenithurai¹,

Chai²

2023

Preprint

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“…Very recently, various TAO-DFT-related extensions, such as TAO-DFT-based ab initio molecular dynamics (TAO-AIMD) [58], TAO-DFT with the polarizable continuum model (TAO-PCM) [59], and a real-time extension of TAO-DFT (RT-TAO-DFT) [54], have been developed, expanding the capabilities of TAO-DFT to handle a more diverse range of applications. Moreover, TAO-DFT has also been adopted to investigate the various properties (e.g., electronic properties [25,[60][61][62][63][64][65][66][67][68], hydrogen storage properties [61,63], spectroscopic properties [58,69,70], and equilibrium thermodynamic properties [58]) of MR systems at the nanoscale.…”

Section: Of 19mentioning

confidence: 99%

Electronic Properties of Graphene Nano-Parallelograms: A TAO-DFT Computational Study

Seenithurai,

Chai

2023

Preprint

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In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally-assisted-occupation density functional theory (TAO-DFT). Our calculations reveal a monotonic decrease in the singlet-triplet energy gap as the GNP length increases. The GNPs possess singlet ground states for all the cases examined. With the increase of GNP length, the vertical ionization potential and fundamental gap decrease monotonically, while the vertical electron affinity increases monotonically. Besides, as the GNP length increases, the symmetrized von Neumann entropy increases monotonically, denoting an increase in the degree of multi-reference character associated with ground-state GNPs. The occupation numbers and real-space representation of active orbitals indicate that there is a transition from the nonradical nature of the shorter GNPs to the increasing polyradical nature of the longer GNPs. In addition, the edge/corner localization of active orbitals is found for the wider and longer GNPs.

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“…The assignments in terms of orbitals are intended to understand the nature of the transition, ligand-centered or charge-transferring. A similar calculation considering 40 excitations (with the triplet state optimized) was used as the basis for the self-consistent two-component spin–orbit coupling TDDFT (SOC-TDDFT) within the ZORA Hamiltonian, where six spin-mixed excitations were calculated using the SR-TDDFT results as the input. , Furthermore, the hybrid B3LYP exchange–correlation functional, with the local density approximation to the correlation functional (which stands for Becke, three-parameter, Lee–Yang–Parr), − was used with the standard Slater-type orbital basis set with the triple-ζ quality double plus polarization function (TZ2P) for all the atoms. The use of hybrid functional in systems containing heavy metals is justified because, in these cases, the introduction of an exact Hartree–Fock exchange rate helps to correct the problem of electronic delocalization, allowing obtaining values for electronic absorption and emission transitions in better agreement with experimental data.…”

Section: Computational Detailsmentioning

confidence: 99%

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

et al. 2022

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Rhenium(I) tricarbonyl complexes have been described as suitable fluorophores, particularly for biological applications. fac-[Re(CO)3(N,N)L](0 or 1+) complexes, where N,N is a substituted dinitrogenated ligand (bipyridine or derivatives with relatively small substituents) and L the ancillary ligand [a pyridine Schiff base (PSB) harboring an intramolecular hydrogen bond (IHB)], have presented promissory results concerning their use as fluorophores, especially for walled cells (i.e., bacteria and fungi). In this work, we present a relativistic theoretical analysis of two series of fac-[Re(CO)3(N,N)PSB]1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2′-bipyridine (bpy) (series A) or 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine (deeb) (series B). We found that all the complexes present absorption in the visible light range. In addition, complexes presenting a PSB with an IHB exhibit luminescent emission suitable for biological purposes: large Stokes shift, emission in the range of 600–700 nm, and τ in the order of 10–2 to 10–3 s. By contrast, complexes with PSB lacking the IHB show a predicted emission with the lowest triplet excited-state energy entering the NIR region. These results suggest a role of the IHB as an important switcher between visible and NIR emissions in this kind of complexes. Since the PSB can be substituted to modulate the properties of the whole Re(I) complex, it will be interesting to explore whether other substitutions can also affect the photophysical properties, mainly the emission range.

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Static Electron Correlation in Anharmonic Molecular Vibrations: A Hybrid TAO-DFT Study

Cited by 8 publications

References 93 publications

TAO-DFT with the Polarizable Continuum Model

TAO-DFT with the Polarizable Continuum Model

Electronic Properties of Graphene Nano-Parallelograms: A TAO-DFT Computational Study

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

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