The relationship between structure and excited-state properties in polyanilines from geminal-based methods

Jahani, Seyedehdelaram; Boguslawski, Katharina; Tecmer, Paweł

doi:10.1039/d3ra05621j

Cited by 7 publications

(6 citation statements)

References 93 publications

(167 reference statements)

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“…Typically, the pCCD molecular orbitals are optimized, ,,, which re-establishes size consistency and yields localized and symmetry-broken orbitals that allow us to simulate quantum states with (quasi-)degeneracies . Numerical examples comprise bond-breaking processes in small molecules, ,,− heavy-element-containing compounds featuring lanthanide or actinide ,,− atoms, organic electronics, , and electronically excited states. ,− ,− Although these numerical studies support pCCD to be a promising alternative to capture static/nondynamic electron correlation effects, − a large fraction of the correlation energy cannot be captured by electron-pair states alone. This missing correlation energy is commonly attributed to so-called broken-pair states.…”

Section: Theorymentioning

confidence: 99%

Benchmarking Ionization Potentials from pCCD Tailored Coupled Cluster Models

Gałyńska,

Boguslawski

2024

J. Chem. Theory Comput.

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The ionization potential (IP) is an important parameter providing essential insights into the reactivity of chemical systems. IPs are also crucial for designing, optimizing, and understanding the functionality of modern technological devices. We recently showed that limiting the CC ansatz to the seniority-zero sector proves insufficient in predicting reliable and accurate ionization potentials within an IP equation-of-motion coupled-cluster formalism. Specifically, the absence of dynamical correlation in the seniority-zero pair coupled cluster doubles (pCCD) model led to unacceptably significant errors of approximately 1.5 eV. In this work, we aim to explore the impact of dynamical correlation and the choice of the molecular orbital basis (canonical vs localized) in CC-type methods targeting 230 ionized states in 70 molecules, comprising small organic molecules, medium-sized organic acceptors, and nucleobases. We focus on pCCD-based approaches as well as the conventional IP-EOM-CCD and IP-EOM-CCSD. Their performance is compared to the CCSD(T) or CCSDT equivalent and experimental reference data. Our statistical analysis reveals that all investigated frozen-pair coupled cluster methods exhibit similar performance, with differences in errors typically within chemical accuracy (1 kcal/mol or 0.05 eV). Notably, the effect of the molecular orbital basis, such as canonical Hartree–Fock or natural pCCD-optimized orbitals, on the IPs is marginal if dynamical correlation is accounted for. Our study suggests that triple excitations are crucial in achieving chemical accuracy in IPs when modeling electron detachment processes with pCCD-based methods.

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Section: Theorymentioning

confidence: 99%

Benchmarking Ionization Potentials from pCCD Tailored Coupled Cluster Models

Gałyńska,

Boguslawski

2024

J. Chem. Theory Comput.

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“…Thus, the underlying electronic structure differs from the conventional picture we obtain when working with delocalized canonical orbitals such as those predicted by DFAs. The significant advantage of a localized basis , is the clear distinction of the donor and acceptor regions or their interfaces . Electronic excitations can be unambiguously assigned to specific molecular basins, allowing dissection of the electronic excitations into, for instance, charge transfer or local ones, while HOMO and LUMO orbitals can be located on, for instance, donor or acceptor domains.…”

Section: Orbital Energiesmentioning

confidence: 99%

“…The significant advantage of a localized basis 104 , 105 is the clear distinction of the donor and acceptor regions or their interfaces. 106 Electronic excitations can be unambiguously assigned to specific molecular basins, allowing dissection of the electronic excitations into, for instance, charge transfer or local ones, while HOMO and LUMO orbitals can be located on, for instance, donor or acceptor domains. Such an analysis is particularly beneficial in designing OPV building blocks that are desired to feature HOMO/LUMO on specified domains or increase the charge-transfer character in the excited states of interest.…”

Section: Interpretational Potentialmentioning

confidence: 99%

Geminal-Based Strategies for Modeling Large Building Blocks of Organic Electronic Materials

Tecmer,

Gałyńska,

Szczuczko

et al. 2023

J. Phys. Chem. Lett.

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We elaborate on unconventional electronic structure methods based on geminals and their potential to advance the rapidly developing field of organic photovoltaics (OPVs). Specifically, we focus on the computational advantages of geminal-based methods over standard approaches and identify the critical aspects of OPV development. Examples are reliable and efficient computations of orbital energies, electronic spectra, and van der Waals interactions. Geminal-based models can also be combined with quantum embedding techniques and a quantum information analysis of orbital interactions to gain a fundamental understanding of the electronic structures and properties of realistic OPV building blocks. Furthermore, other organic components present in, for instance, dye-sensitized solar cells (DSSCs) represent another promising scope of application. Finally, we provide numerical examples predicting the properties of a small building block of OPV components and two carbazole-based dyes proposed as possible DSSC sensitizers.

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“…Some of the most promising ones are those based on the pCCD ansätze. − They have seen recent successes in treating strongly correlated systems with mean-field-like scaling. pCCD has the feature of using its optimized orbital basis without defining active spaces. ,− The size-extensive and size-consistent nature of orbital-optimized pCCD has motivated a wide range of studies for covalent molecules, − noncovalent systems, , and excited states, − including organic systems. , Perturbation theory-based, and linearized coupled cluster (LCC) corrections have also been successfully added to the pCCD wave function to improve the description of dynamic correlation. − …”

Section: Introductionmentioning

confidence: 99%

“… 51 , 54 − 56 The size-extensive and size-consistent nature of orbital-optimized pCCD has motivated a wide range of studies for covalent molecules, 54 − 63 noncovalent systems, 64 , 65 and excited states, 66 − 69 including organic systems. 70 , 71 Perturbation theory-based, and linearized coupled cluster (LCC) corrections have also been successfully added to the pCCD wave function to improve the description of dynamic correlation. 72 − 77 …”

Section: Introductionmentioning

confidence: 99%

Toward Reliable Dipole Moments without Single Excitations: The Role of Orbital Rotations and Dynamical Correlation

Chakraborty,

de Moraes,

Boguslawski

et al. 2024

J. Chem. Theory Comput.

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The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used to assess the accuracy and reliability of new electronic structure methods. This work analyses electronic dipole moments computed with the pair coupled cluster doubles (pCCD) ansaẗze and its linearized coupled cluster (pCCD-LCC) corrections using the canonical Hartree− Fock and pCCD-optimized (localized) orbital bases. The accuracy of pCCD-based dipole moments is assessed against experimental and CCSD(T) reference values using relaxed and unrelaxed density matrices and different basis set sizes. Our test set comprises molecules of various bonding patterns and electronic structures, exposing pCCD-based methods to a wide range of electron correlation effects. Additionally, we investigate the performance of pCCD-in-DFT dipole moments of some model complexes. Finally, our work indicates the importance of orbital relaxation in the pCCD model and shows the limitations of the linearized couple cluster corrections in predicting electronic dipole moments of multiple-bonded systems. Most importantly, pCCD with a linearized CCD correction can reproduce the dipole moment surfaces in singly bonded molecules, which are comparable to the multireference ones.

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The relationship between structure and excited-state properties in polyanilines from geminal-based methods

Abstract: We employ pCCD-based methods to study the structure-to-property relationship in polyanilines (PANIs) of different lengths and oxidation states.

Cited by 7 publications

References 93 publications

Benchmarking Ionization Potentials from pCCD Tailored Coupled Cluster Models

Benchmarking Ionization Potentials from pCCD Tailored Coupled Cluster Models

Geminal-Based Strategies for Modeling Large Building Blocks of Organic Electronic Materials

Toward Reliable Dipole Moments without Single Excitations: The Role of Orbital Rotations and Dynamical Correlation

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