First-principles calculations of anharmonic and deuteration effects on the photophysical properties of polyacenes and porphyrinoids

Valiev, Rashid R.; Nasibullin, Rinat T.; Cherepanov, Victor N.; Baryshnikov, Glib; Sundholm, Dage; Ågren, Hans; Минаев, Б. Ф.; Kurtén, Theo

doi:10.1039/d0cp03231j

Cited by 40 publications

(61 citation statements)

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“…In the case of the former, works combining the efforts of Plotnikov, Robinson and Jortner at the INDO level have shown some success in treating this mechanism semiempirically [24][25][26][27] . However, the combination of this framework with time-dependent density functional theory (TDDFT) yielded much more accurate rate constant calculations [28][29][30] , which we call the Plotnikov-Robinson-Jortner (PRJ) formalism. However, in the case of the latter bosonic configuration problem, the difficulty boils down to the fact that no known polynomial-time algorithm offers an exact solution 31 .…”

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

“…It should be noted that nowhere else in the literature is a similar bosonic calculation implemented, as this problem is analogous to the 0-1 Knapsack problem in mathematics. Valiev and co-workers 30 have recently discussed a solution to the problem through the use of a Lagrangian multiplier to estimate the most probable vibronic configuration, offering valuable insight into the problem. Here, a similar framework has been implemented.…”

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

“…For this, we consider the full Hessian of the initial singlet excited state in addition to the ICV 30 . Making the same assumptions as per Equation 10, we arrive at: This is the author's peer reviewed, accepted manuscript.…”

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

“…in a similar way to that of Valiev and co-workers 30 , where λ is the Lagrange multiplier, rounding to the nearest integer, since the solution is rarely discrete. We can then expand about this maximum, computationally shifting the problem to a polynomial series.…”

Section: Configuration Space Computationmentioning

confidence: 99%

“…Recently, Valiev and co-workers 30 noted the importance of anharmonic effects to the overall IC rate constant. They found that by considering anharmonicity, the rate constant for Naphthalene increased by several orders of magnitude.…”

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

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Modeling radiative and non-radiative pathways at both the Franck–Condon and Herzberg–Teller approximation level

Manian¹,

Shaw

Lyskov³

et al. 2021

The Journal of Chemical Physics

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Here, we present a concise model which can predict the photoluminescent properties of a given compound from first principles, both within and beyond the Franck-Condon approximation. The formalism required to compute fluorescence, Internal Conversion (IC), and Inter-System Crossing (ISC) is discussed. The IC mechanism in particular is a difficult pathway to compute due to difficulties associated with the computation of required bosonic configurations and non-adiabatic coupling elements. Here, we offer a discussion and breakdown on how to model these pathways at the Density Functional Theory (DFT) level, with respect to its computational implementation, strengths and current limitations. The model is then used to compute the photoluminescent quantum yield (PLQY) of a number of small but important compounds: Anthracene, Tetracene, Pentacene, diketo-pyrrolo-pyrrole (DPP), and Perylene Diimide (PDI), within a polarizable continuum model. Rate constants for fluorescence, IC, and ISC compare well for the most part with respect to experiment, despite triplet energies being overestimated to a degree. The resulting PLQYs are promising with respect to the level of theory being DFT. While we obtained a positive result for PDI within the Franck-Condon limit, the other systems require a second order correction. Recomputing quantum yields with Herzberg-Teller terms yields PLQYs of 0.19, 0.08, 0.04, 0.70, and 0.99 for Anthracene, Tetracene, Pentacene, DPP, and PDI respectively. Based on these results, we are confident the presented methodology is sound with respect to the level of quantum chemistry, and presents an important stepping stone in the search for a tool to predict properties of larger, coupled systems.

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Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

Section: Configuration Space Computationmentioning

confidence: 99%

Section: Please Cite This Article As Doi:101063/50058643mentioning

confidence: 99%

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Modeling radiative and non-radiative pathways at both the Franck–Condon and Herzberg–Teller approximation level

Manian¹,

Shaw

Lyskov³

et al. 2021

The Journal of Chemical Physics

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Effect of choosing coordinate systems on computationally predicting nonradiative transition rates of flexible thermally activated delayed fluorescence molecules

Min,

Kim,

Kim

et al. 2023

Bulletin Korean Chem Soc

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Understanding nonradiative transition mechanisms is important in various situations. However, compared with radiative processes where temporal profiles of photon emission can be monitored in a straightforward manner, experimentally accessing the rate information may not be an easy task with nonradiative transitions. Hence, applying theoretical tools toward predicting the rates can be a useful tactic. Such predictions become very useful in designing optoelectronic materials as in the molecules adopted for constructing organic light‐emitting diodes (OLEDs). The correlation function formalism is a method that can fulfill the purpose of designing OLED materials. The formalism requires information regarding the vibrational normal modes of the two electronic states before and after the transition. Because the method is also based on harmonic oscillator approximation, it can actually fail to provide high reliability when there is a large geometric distortion between the initial and the final states. In fact, the harmonic normal mode picture is more prone to lose reliability in the Cartesian coordinates than in the internal ones even at a small distortion, and hence adopting internal coordinates may be more preferable for practical calculations. This is because normal mode mixing becomes less severe when molecular coordinates are described with internal degrees of freedom such as bond stretching, bending, and torsion. In this regard, how much more reliable the nonradiative rate predictions in OLED materials become with the use of internal coordinate system deserves a close inspection. In this account, we review on the derivation of the correlation function formalism and provide how it can be adapted toward the use of the internal coordinates. As a demonstration, we evaluate the intersystem crossing and the internal conversion rates of a series of thermally activated delayed fluorescence (TADF) molecules with both Cartesian and internal coordinate systems. Overall, handling transitions involving substantial structural changes is improved indeed with the internal coordinates. However, limitations are still apparent for the TADF systems with a flexible donor–acceptor type construct especially when the inevitable inter‐domain twisting takes place with the electronic transition. Future prospect for handling the issue is commented as a concluding remark.

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Computational study of IR, Raman, and NMR spectra of 4-methylmethcathinone drug

et al. 2021

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First-principles calculations of anharmonic and deuteration effects on the photophysical properties of polyacenes and porphyrinoids

Abstract: A new method for calculating internal conversion rate constants (kIC), including the anharmonic effects, and using the lagrangian multiplier technique, is proposed. The deuteration effect on kIC was investigated for...

Cited by 40 publications

References 64 publications

Modeling radiative and non-radiative pathways at both the Franck–Condon and Herzberg–Teller approximation level

Modeling radiative and non-radiative pathways at both the Franck–Condon and Herzberg–Teller approximation level

Effect of choosing coordinate systems on computationally predicting nonradiative transition rates of flexible thermally activated delayed fluorescence molecules

Computational study of IR, Raman, and NMR spectra of 4-methylmethcathinone drug

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