Studies of the Ground and Excited-State Surfaces of the Retinal Chromophore using CAM-B3LYP

Rostov, I.V.; Amos, Roger D.; Kobayashi, Rika; Scalmani, Giovanni; Frisch, Michael J.

doi:10.1021/jp911329g

Cited by 84 publications

(62 citation statements)

References 71 publications

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“…The picture that emerges from a structural analysis is not surprising for the CASPT2 and CC2 results as this is in agreement with studies by Valsson and Filippi, Send and Sundholm, Rostov et al ., and Tuna et al What is remarkable about these data is that the CASSCF method provides essentially identical excited‐state bond length pattern as found with CASPT2 approach for both in‐plane (locked‐11.5) and twisted [locked‐11.7 (twist), 9,10‐dimethyl] molecular structures of PSB5 analogues in vacuo . In addition, CASSCF‐based BLAs are only within 0.011 Å of the CASPT2 ones.…”

Section: Resultssupporting

confidence: 54%

Excited‐state minima and emission energies of retinal chromophore analogues: Performance of CASSCF and CC2 methods as compared with CASPT2

et al. 2017

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This study provides gas-phase S excited-state geometries along with emission and adiabatic energies for methylated/demethylated and ring-locked analogues of protonated Schiff base retinal models comprising system of five conjugated double bonds (PSB5), using second order multiconfiguration perturbation theory (CASPT2). CASPT2 results serve as reference data to assess the performance of CC2 (second-order approximate coupled cluster singles and doubles) and a commonly used CASSCF/CASPT2 protocol, that is, complete active space self-consistent field (CASSCF) geometry optimization followed by CASPT2 energy calculation. We find that the CASSCF methodology fails to locate planar S minimum energy structures for four out of five investigated planar models in contrast to CC2 and CASPT2 methods. However, for those which were found: one planar and two twisted minima, there is an excellent agreement between CASSCF and CASPT2 results in terms of geometrical parameters, one-electron properties, as well as emission and adiabatic energies. CC2 performs well for in-plane S minima and their spectroscopic and electronic properties. However, this picture deteriorates for twisted minima. As expected, the CC2 description of the S electronic state, with strong multireference and significant double excitation character, is very poor, exhibiting errors in transition energies exceeding 1 eV. They may be substantially diminished by recalculating transition energies with CASPT2 method. Our work shows that CASSCF/CASPT2 and CC2 shortcomings may influence gas-phase retinal analogues' excited state description in a dramatic way. © 2017 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 54%

Excited‐state minima and emission energies of retinal chromophore analogues: Performance of CASSCF and CC2 methods as compared with CASPT2

et al. 2017

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“…The primary goal of this study is to shed some light on this issue by employing recently proposed long–range corrected density functional theory (hereafter denoted as LRC–DFT) to compute charge–transfer integrals. The LRC–DFT is still being extensively tested primarily with an eye toward electric dipole (hyper)polarizabilities, linear and nonlinear optical spectra [17–29]. Here, we use two LRC functionals, namely LC-BLYP [30] and CAM–B3LYP [31] together with their conventional counterparts.…”

Section: Introductionmentioning

confidence: 99%

Long-range corrected DFT calculations of charge-transfer integrals in model metal-free phthalocyanine complexes

et al. 2010

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An assessment of several widely used exchange--correlation potentials in computing charge-transfer integrals is performed. In particular, we employ the recently proposed Coulomb-attenuated model which was proven by other authors to improve upon conventional functionals in the case of charge-transfer excitations. For further validation, two distinct approaches to compute the property in question are compared for a phthalocyanine dimer.

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“…The ground‐state geometry and the electronic excited states of Pt‐NI‐Py were calculated by DFT and time‐dependent DFT (TDDFT) methods with the Gaussian 09W software . Owing to the charge‐transfer process and the presence of the heavy platinum atom, the CAM‐B3LYP/GENECP functional was selected for the calculations …”

Section: Resultsmentioning

confidence: 99%

An N^N Platinum(II) Bis(acetylide) Complex with Naphthalimide and Pyrene Ligands: Synthesis, Photophysical Properties, and Application in Triplet–Triplet Annihilation Upconversion

Zhong

Zhao

2017

Eur J Inorg Chem

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Two different chromophores, pyrene (Py) and naphthalimide (NI), were introduced as acetylide ligands in a heteroleptic diimine N^N PtII bis(acetylide) complex (Pt‐NI‐Py) to broaden the absorption bands and enable the intramolecular energy‐transfer process. Steady‐state and transient spectroscopy were used to study the photophysical properties of the complexes. The lowest triplet state of Pt‐NI‐Py (τT = 34 µs) is localized on the pyrene part, although the singlet‐state energy level of the naphthalimide unit is lower. Intramolecular energy‐transfer processes were observed. Moreover, Pt‐NI‐Py shows enhanced visible‐light harvesting compared with the bis(pyrenylacetylide) complex (Pt‐Py) and a lower triplet‐state energy level than that of the bis(ethynylnaphthalimide) complex (Pt‐NI). The results demonstrate that the relative energy levels of the singlet excited states of the different chromophores do not agree with the relative energy levels of the triplet states of the same chromophores. Efficient triplet‐state generation (ΦΔ = 0.8) gives Pt‐NI‐Py a high triplet–triplet annihilation (TTA) upconversion efficiency (34 %).

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Studies of the Ground and Excited-State Surfaces of the Retinal Chromophore using CAM-B3LYP

Cited by 84 publications

References 71 publications

Excited‐state minima and emission energies of retinal chromophore analogues: Performance of CASSCF and CC2 methods as compared with CASPT2

Excited‐state minima and emission energies of retinal chromophore analogues: Performance of CASSCF and CC2 methods as compared with CASPT2

Long-range corrected DFT calculations of charge-transfer integrals in model metal-free phthalocyanine complexes

An N^N Platinum(II) Bis(acetylide) Complex with Naphthalimide and Pyrene Ligands: Synthesis, Photophysical Properties, and Application in Triplet–Triplet Annihilation Upconversion

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