The Intriguing Case of the One‐Photon and Two‐Photon Absorption of a Prototypical Symmetric Squaraine: Comparison of TDDFT and Wave‐Function Methods

Ferrer, Francisco J. Avila; Angeli, Celestino; Cerezo, Javier; Coriani, Sonia; Ferretti, Alessandro; Santoro, Fabrizio

doi:10.1002/cptc.201900121

Cited by 9 publications

(8 citation statements)

References 79 publications

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“…As ADC(3) enjoys a lower formal computational scaling [ ] than CC3 [ ], and is generally regarded as the logical path for improvement over ADC(2), this finding contributed to enhancing the popularity of ADC(3) in the electronic structure community. ADC(3) was subsequently employed to perform theory versus experiment comparisons − and to define benchmark values for assessing lower-order methods. − …”

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confidence: 99%

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Loos

Jacquemin

2020

J. Phys. Chem. Lett.

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The search for new models rapidly delivering accurate excited-state energies and properties is one of the most active research lines of theoretical chemistry. Along with these developments, the performance of known methods is constantly reassessed on the basis of new benchmark values. In this Letter, we show that the third-order algebraic diagrammatic construction, ADC(3), does not yield transition energies of the same quality as the third-order coupled cluster method, CC3. This is demonstrated by extensive comparisons with several hundred high-quality vertical transition energies obtained with FCI, CCSDTQ, and CCSDT. Direct comparisons with experimental 0–0 energies of small- and medium-size molecules support the same conclusion, which holds for both valence and Rydberg transitions. Considering these results, we introduce a composite approach, ADC(2.5), which consists of averaging the ADC(2) and ADC(3) excitation energies. Although ADC(2.5) does not match the CC3 accuracy, it significantly improves the ADC(3) results, especially for vertical energies.

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mentioning

confidence: 99%

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Loos

Jacquemin

2020

J. Phys. Chem. Lett.

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“…As ADC(3) enjoys a lower formal computational scaling [O(N 6 )] than CC3 [O(N 7 )], and is generally regarded as the logical path for improvement over ADC (2), this finding contributed to enhance the popularity of ADC(3) in the electronic structure community. ADC(3) was subsequently employed to perform theory vs experiment comparisons, [20][21][22][23][24][25][26] and to define benchmark values for assessing lower-order methods. [27][28][29][30] Given, on the one hand, that ADC(3) was advocated as a benchmark method and, on the other hand, the recent availability of high-accuracy reference energies for a large panel of ES, 18,31,32 we believe that the time has come to perform a new performance assessment of this method.…”

mentioning

confidence: 99%

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Loos¹,

Jacquemin²

2019

Preprint

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The search for new ab initio models rapidly delivering accurate excited state energies and properties is one of the most active research lines of theoretical chemistry. Along with these methodological developments, the performances of known methods are constantly reassessed thanks to the emergence of new benchmark values. In this Letter, we show that, in contrast to previous claims, the third-order algebraic diagrammatic construction, ADC(3), does not yield transition energies of the same quality as the third-order coupled cluster method, CC3. There is indeed a significant difference in terms of accuracy between the two approaches, as we clearly and unambiguously demonstrate here thanks to extensive comparisons with several hundreds high-quality vertical transition energies obtained with FCI, CCSDTQ, and CCSDT. Direct comparisons with experimental 0-0 energies of small-and medium-size organic molecules support the same conclusion, which holds for both valence and Rydberg transitions, as well as singlet and triplet states. In regards of these results, we introduce a composite approach that we named ADC(2.5) which consists in averaging the ADC(2) and ADC(3) excitation energies. Although ADC(2.5) does not match the CC3 accuracy, it significantly improves the ADC(3) results, especially for vertical energies. We hope that the present contribution will stimulate further developments and, in particular, improvements of the ADC-type methods which have the indisputable advantage of being computationally lighter than their equivalent-order CC variants.

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“…Since the bis(N,N-dimethylamine) squaraine molecule represents the challenge for the computational methods due to the double excitation effects balanced with the charge transfer and moderate biradicaloid character, the literature recommendations have been applied for the computational methodology for the electronic excitations (Quartarolo et al, 2009;Alberto et al, 2014;Bassal et al, 2017;Ferrer et al, 2019). It has been proven that the conventional long-range-corrected functionals correctly predict the one-photon absorption spectrum of bis(N,N-dimethylamine) squaraine and despite strong overestimation of the energy of the states involved in two-photon transitions allow the correct assignment of the experimentally observed states.…”

Section: Methodsmentioning

confidence: 99%

“…The presence of the D-A-D motif may lead to the efficient two-photon absorption (TPA) of squaraine systems. The simple symmetrical dibutylaniline squaraine dye (SQ) has been shown to exhibit the strong two-photon absorption with three bands: vibronic coupling band of the TPA cross section equal to 200 GM, second band at 850 nm with σ TPA 2000 GM corresponding to the S 2 excited state, and the third one at 700 nm with the cross section of 15,000 GM is governed by the excitation to the S 4 state (Webster et al, 2010;Ferrer et al (2019)). Squaraines of the extremely large values of σ TPA have been obtained (for instance, 27 ,000 GM for heterocyclic pyrrolesubstituted squaric acid ring) (Pawlicki et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

“…One need to underline that the prototypical dimethylaniline squaraine dye is challenging from the theoretical point of view due to the interplay of several competing effects: the charge transfer between the electron-accepting central squaric acid ring and the electron-donating side groups, the mild biradicaloid character, and the significant double excitations affecting the two-photon theoretical description (Prabhakar et al, 2005b;Prabhakar et al, 2010;Prabhakar et al, 2005a;Yesudas et al, 2006;Srinivas et al, 2007;Ferrer et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

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Supramolecular Approach to Tuning the Photophysical Properties of Quadrupolar Squaraines

et al. 2022

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In the present study, the influence of the hydrogen bonding for the one- and two-photon absorption of the prototypical squaraine dye is investigated with quantum chemistry tools. The central squaraine unit is bound by strong hydrogen bonds with 4-substituted N,N′-diphenylurea and, alternatively, N,N′-diphenylthiourea molecules, which affects to a high extend the properties of the squaraine electron accepting moiety, thus shifting its maximum absorption wavelength and enhancing the TPA cross section. The replacement of oxygen by sulfur atoms in the squaraine central ring, known to affect its photophysical behavior, is considered here as the way of modifying the strength and nature of the intermolecular contacts. Additionally, the influence of the oxygen-by-sulfur replacement is also considered in the N,N′-diphenylurea moiety, as the factor affecting the acidity of the N–H protons. The introduction of the sequence of the substituents of varying electron-donating or electron-withdrawing characters in the position 4 of N,N′-diphenyl(thio)urea subsystems allows to finely tune the hydrogen bonding with the central squaraine unit by further modification of the N–H bond characteristics. All of these structural modifications lead to the controlled adjustment of the electron density distribution, and thus, the properties affected such as transition moments and absorption intensity. Ab initio calculations provide strong support for this way of tailoring of one- or two-photon absorption due to the obtained strong hypsochromic shift of the maximum one-photon absorption wavelength observed particularly for thiosquaraine complexes and an increase in the TPA wavelength together with the increase in the TPA cross section. Moreover, the source of the strong modification of the thiosquaraine OPA in contrast to the pristine oxosquaraine upon N,N′-diphenyl(thio)urea substitution is determined. Furthermore, for the first time, the linear dependence of the non-additivity in the interaction energy on the Hammett substituent constant is reported. The stronger the electron-donating character of the substituent, the larger the three-body non-additive components and the larger their percentage to the total interaction energy.

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The Intriguing Case of the One‐Photon and Two‐Photon Absorption of a Prototypical Symmetric Squaraine: Comparison of TDDFT and Wave‐Function Methods

Cited by 9 publications

References 79 publications

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?

Supramolecular Approach to Tuning the Photophysical Properties of Quadrupolar Squaraines

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