Ionization Energies and Dyson Orbitals of the Iso-electronic SO2, O3, and S3 Molecules from Electron Propagator Calculations

Pawłowski, Filip; Ortiz, J. V.

doi:10.1021/acs.jpca.1c01759

Cited by 6 publications

(9 citation statements)

References 82 publications

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“…A similar agreement is obtained for the 2 Π final state of HCN + , whereas the result of Krause et al pertains to 2 Σ. The VIE of SO 2 calculated by the latter authors pertains to the second excited state ( 2 A 2 ) of the cation, whereas the value reported by Bruneval et al for the correct, 2 A 1 final state agrees with recent high-accuracy calculations − and photoelectron experiments . BD-T1 calculations agree with Bruneval et al that the lowest state of BN + is 2 Π, not 2 Σ.…”

Section: Improved Gw100 δCcsd(t) Benchmarkssupporting

confidence: 85%

“…The BD-T1 method’s employment of an approximate Brueckner reference determinant endows it with greater predictive capabilities for highly correlated initial states. This capability was amply demonstrated in recent applications to diradicaloid ozone, iso-electronic SO 2 and S 3 molecules, and double Rydberg anions. ,− ,,,,, …”

Section: Bd-t1 Benchmarksmentioning

confidence: 99%

“…This capability was amply demonstrated in recent applications to diradicaloid ozone, iso- electronic SO 2 and S 3 molecules, and double Rydberg anions. 9,[23][24][25]27,28,68,87,90…”

Section: Bd-t1 Benchmarksmentioning

confidence: 99%

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Electron Propagator Self-Energies versus Improved GW100 Vertical Ionization Energies

Opoku

Pawłowski

Ortiz

2022

J. Chem. Theory Comput.

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Ab initio electron propagator (EP) methods that are free of adjustable parameters in their self-energy formulae and in the generation of their orbital bases have been applied to the calculation of the lowest vertical ionization energies (VIEs) of the GW100 set. An improved set of standard results accompanied by irreducible representation assignments has been produced indirectly with coupled-cluster singles and doubles plus perturbative triples, i.e., CCSD(T), total energy differences at initial-state geometries reoptimized (in 28 cases) with the largest applicable point groups. The best compromises of accuracy and efficiency belong to a new generation of EP self-energies, several members of which may be derived from an intermediately normalized, Hermitized super-operator metric. The following diagonal self-energy methods are optimal: opposite-spin non-Dyson second order (os-nD-D2), approximately renormalized partial third order (P3+), approximately renormalized quasiparticle third order (Q3+), and non-Dyson approximately renormalized linear third order version B (nD-L3+B). Their mean absolute errors (MAEs) in electron volts and arithmetic scaling factors expressed in terms of occupied (O) and virtual (V) orbital dimensions are, respectively, (0.18, OV2), (0.14, O2V3), (0.15, O2V3), and (0.11, OV4). The 0.06 eV MAE for the non-diagonal, sixth-power (O2V4) Brueckner doubles, triple-field operator (BD-T1) EP method is exceeded by the 0.1 eV MAE with respect to experiments in seventh-power, ΔCCSD(T) calculations and indicates that BD-T1 may serve as a direct, spin-symmetry-conserving alternative in the generation of standard results for VIEs of larger, closed-shell molecules.

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Section: Improved Gw100 δCcsd(t) Benchmarkssupporting

confidence: 85%

Section: Bd-t1 Benchmarksmentioning

confidence: 99%

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Electron Propagator Self-Energies versus Improved GW100 Vertical Ionization Energies

Opoku

Pawłowski

Ortiz

2022

J. Chem. Theory Comput.

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“…The SOCs can be expressed as , normalS normalO normalC i j = ∑ n false| ⟨ ψ S i false| Ĥ normalS normalO false| ψ T j , n ⟩ false| 2 ; goodbreak0em1em⁣ n = x , y , z Here, Ĥ normalS normalO represents the spin–orbit Hamiltonian. The SOC constants are calculated through the PySOC program unified with TDDFT in Gaussian 16 …”

Section: Methodsmentioning

confidence: 99%

Theoretical Investigation of Ru(II) Complexes with Long Lifetime and a Large Two-Photon Absorption Cross-Section in Photodynamic Therapy

et al. 2023

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Two-photon photodynamic therapy (TP-PDT), as a new method for cancer, has shown unique advantages in tumors. A low two-photon absorption cross-section (δ) in the biologic spectral window and a short triplet state lifetime are the important issues faced by the current photosensitizers (PSs) in TP-PDT. In this paper, the photophysical properties of a series of Ru(II) complexes were studied by density functional theory and time-dependent density functional theory methods. The electronic structure, one- and two-photon absorption properties, type I/II mechanisms, triplet state lifetime, and solvation free energy were calculated. The results showed that the substitution of methoxyls by pyrene groups greatly improved the lifetime of the complex. Furthermore, the addition of acetylenyl groups subtly enhanced δ. Overall, complex 3b possess a large δ(1376 GM), a long lifetime (136 μs), and better solvation free energy. It is hoped that it can provide valuable theoretical guidance for the design and synthesis of efficient two-photon PSs in the experiment.

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“…In this paper, all calculations are performed in the Gaussian 16 package . The ground-state geometries of all complexes are optimized by DFT method, and the frequencies of each optimized structure are calculated.…”

Section: Methodologiesmentioning

confidence: 99%

Photophysical Exploration of Zn(II) Polypyridine Photosensitizers in Two-Photon Photodynamic Therapy: Insights from Theory

Xue

Guo

et al. 2022

Inorg. Chem.

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The high incidence and difficulties of treatment of cancer have always been a challenge for mankind. Two-photon photodynamic therapy (TP-PDT) as a less invasive technique provides a new perspective for tumor treatment due to its low-energy near-infrared excitation, high targeting, and minor damage. At present, the emerging metal complexes used as the photosensitizers (PSs) in TP-PDT have aroused great interest. However, most metal complexes as PSs in TP-PDT still face some problems, such as slow clearance, unsatisfactory two-photon absorption (TPA) characteristics, high price, low reactivity, and poor solubility. In this work, density functional theory and time-dependent density functional theory were used to characterize the one/two-photon response, solvation free energy, and lipophilicity of a series of novel PSs applied in TP-PDT. The results suggest that based on complex 1, replacing Ru(II) center with Zn(II) (complex 2) can effectively prolong the triplet excited state lifetime while reducing the cost and environmental pollution, and the azetidine heterospirocycles were introduced into the ligand scaffold (complex 3), which effectively reduced the vibration relaxation of the ligand group and improved the water solubility; further, the addition of acetylenyl groups subtly enhanced the light absorption and significantly improved the two-photon response (complex 4). In addition, all complexes met the requirement of a PS and could be used as potential candidates for TP-PDT. In particular, complex 4 has the advantages of high solvation free energy, a large TPA cross-section (1413 GM), a long triplet state lifetime (671 μs), good chemical reactivity, and low cost, and it is easy to be scavenged by organisms. Overall, this contribution may provide an important clue to formulate clear design principles for type I/II PSs and rational design of PSs with high intersystem crossing rates, a long lifetime, and therapeutic excitation wavelengths.

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Ionization Energies and Dyson Orbitals of the Iso-electronic SO₂, O₃, and S₃ Molecules from Electron Propagator Calculations

Cited by 6 publications

References 82 publications

Electron Propagator Self-Energies versus Improved GW100 Vertical Ionization Energies

Electron Propagator Self-Energies versus Improved GW100 Vertical Ionization Energies

Theoretical Investigation of Ru(II) Complexes with Long Lifetime and a Large Two-Photon Absorption Cross-Section in Photodynamic Therapy

Photophysical Exploration of Zn(II) Polypyridine Photosensitizers in Two-Photon Photodynamic Therapy: Insights from Theory

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