Exploring excited states using Time Dependent Density Functional Theory and density-based indexes

Adamo, Carlo; Bahers, Tangui Le; Savarese, Marika; Wilbraham, Liam; García, Gregorio; Fukuda, Ryoichi; Ehara, Masahiro; Rega, Nadia; Ciofini, Ilaria

doi:10.1016/j.ccr.2015.03.027

Cited by 125 publications

(125 citation statements)

References 70 publications

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“…A better comparison of the results can be achieved by inspecting the Mulliken charges on the iridium atom q Ir . For the ground state, a variation from 1.20 to 1.30 is observed when going from CASSCF (12,9) to MR-CIS (12,12). For the first and second excited states the opposite trend is observed and the CASSCF method gives higher charges.…”

Section: Mr-cisd(87)/d (mentioning

confidence: 73%

“…31). For example, in the case of the 1 1 A → 2 1 A transition the charge transferred from iridium to the ligands amounts to 0.46 e in the case of CASSCF (12,9) while only half of this value is obtained for MR-CIS (12,9). The 4 1 A states generally possess reduced MLCT character and again some discrepancies between the methods are observed.…”

Section: Mr-cisd(87)/d (mentioning

confidence: 93%

“…As shown in Table II, already the excitation energies of these states exhibit strong deviations depending on the method used. The 2 1 A energies vary between 4.17 eV for CASSCF(12,9) and 3.56 eV for CASSCF (12,12), and in the case of the 4 1 A state the difference between CASSCF(12,9) and MR-CIS(12,12) exceeds 1 eV. These excited states are combinations of ligandcentered (LC) and metal-to-ligand charge transfer (MLCT) states.…”

Section: Mr-cisd(87)/d (mentioning

confidence: 99%

“…40,41 Therefore, two active spaces (using 12 electrons in either 9 or 12 orbitals) and two different excitation levels are considered. Overall, we have performed CASSCF (12,9), CASSCF (12,12), MR-CIS (12,9), and MR-CIS (12,12) calculations, in connection with the LANL2DZ pseudopotential. 42,43 In all cases state-averaging over the lowest ten singlet states, corresponding to four states of A and six of E symmetry, is carried out.…”

Section: Mr-cisd(87)/d (mentioning

confidence: 99%

“…[1][2][3] However, the assignment of state characters based on orbitals alone is challenging in many cases, e.g., when the orbital character is not clearly visible, when the orbitals are delocalized, when many configurations are involved, or when partial double excitation character is present. To overcome some of these problems, different phenomenological descriptors have been introduced that monitor diverse specific properties, such as the number of unpaired electrons, 4-6 double excitation character, 3,7 charge transfer, [8][9][10][11][12] excitonic effects, [13][14][15] collectivity, 16 entanglement, 17,18 and orbital relaxation. 19 While these certainly provide important insight, the sheer number of such descriptors shows how challenging it is to grasp many-electron wavefunctions in their full complexity.…”

mentioning

confidence: 99%

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Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps

Plasser

González

2016

The Journal of Chemical Physics

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A simple and powerful method for comparing many-electron wavefunctions constructed at different levels of theory is presented. By using wavefunction overlaps, it is possible to analyze the effects of varying wavefunction models, molecular orbitals, and one-electron basis sets. The computation of wavefunction overlaps eliminates the inherent ambiguity connected to more rudimentary wavefunction analysis protocols, such as visualization of orbitals or comparing selected physical observables. Instead, wavefunction overlaps allow processing the many-electron wavefunctions in their full inherent complexity. The presented method is particularly effective for excited state calculations as it allows for automatic monitoring of changes in the ordering of the excited states. A numerical demonstration based on multireference computations of two test systems, the selenoacrolein molecule and an iridium complex, is presented.

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Section: Mr-cisd(87)/d (mentioning

confidence: 73%

Section: Mr-cisd(87)/d (mentioning

confidence: 93%

Section: Mr-cisd(87)/d (mentioning

confidence: 99%

Section: Mr-cisd(87)/d (mentioning

confidence: 99%

mentioning

confidence: 99%

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Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps

Plasser

González

2016

The Journal of Chemical Physics

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Optically Active A‐Shaped Cyclic Molecules Based on Planar Chiral [2.2]Paracyclophanes Emitting Bright Circularly Polarized Luminescence with High Anisotropy Factors

Matsumura,

Inoue,

Morisaki

2023

Adv Funct Materials

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Optically active A‐shaped cyclic molecules are synthesized by incorporating a planar chiral [2.2]paracyclophane unit to form a helical structure. These molecules exhibit large molar absorption coefficients, moderate photoluminescence (PL) quantum efficiencies, and high circularly polarized luminescence (CPL) anisotropy factors, resulting in high CPL brightness values (BCPL values). According to the time‐dependent density functional theory (TD‐DFT) theoretical studies, extended π‐conjugated moieties act as light‐harvesting units, and emissions occur from the helical skeletons. The TD‐DFT calculations reproduce the experimentally determined absorption, PL, circular dichroism, and CPL properties of the A‐shaped cyclic molecules.

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Theoretical Insights for Materials Properties of Cyclic Organic Nanorings

Pérez-Jiménez

Sancho-García

2020

Advcd Theory and Sims

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The synthesis of new carbon nanoforms with remarkable and fine-tuned bulk properties still represents a formidable challenge, with cyclic organic nanorings emerging in recent years for the template-driven design of this kind of systems. The design and engineering of these materials can be first controlled at the molecular scale, to further induce their specific self-assembly toward tailored properties at the nanoscale. Theoretical studies have lately contributed to the understanding of the underlying physical effects, the development of synthetic strategies, and the rationalization of novel materials properties, employing a variety of methods ranging from accurate calculations of isolated molecules to atomistic molecular dynamics simulations of a large sample of molecules in realistic conditions, which will be reviewed here with a focus on the transition from single-molecule to supramolecular properties.

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Exploring excited states using Time Dependent Density Functional Theory and density-based indexes

Cited by 125 publications

References 70 publications

Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps

Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps

Optically Active A‐Shaped Cyclic Molecules Based on Planar Chiral [2.2]Paracyclophanes Emitting Bright Circularly Polarized Luminescence with High Anisotropy Factors

Theoretical Insights for Materials Properties of Cyclic Organic Nanorings

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