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

Author(s): R. R. Valiev ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵ , R. T. Nasibullin ⁶ ^, ⁷ ^, ⁸ ^, ⁹ , V. N. Cherepanov ⁶ ^, ⁷ ^, ⁸ ^, ⁹ , G. V. Baryshnikov ¹⁰ ^, ¹¹ ^, ¹² ^, ¹³ ^, ¹⁴ , D. Sundholm ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵ , H. Ågren ¹⁰ ^, ¹¹ ^, ¹² ^, ¹³ ^, ¹⁴ , B. F. Minaev ¹⁰ ^, ¹¹ ^, ¹² ^, ¹³ ^, ¹⁴ , T. Kurtén ¹ ^, ² ^, ³ ^, ⁴ ^, ⁵

Publication date (Electronic): 2020

Journal: Physical Chemistry Chemical Physics

Publisher: Royal Society of Chemistry (RSC)

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Abstract

A new method for calculating internal conversion rate constants ( k _IC), including anharmonic effects and using the Lagrangian multiplier technique, is proposed.

Abstract

A new method for calculating internal conversion rate constants ( k̲ _IC), including anharmonic effects and using the Lagrangian multiplier technique, is proposed. The deuteration effect on k̲ _IC is investigated for naphthalene, anthracene, free-base porphyrin ( H2P) and tetraphenylporphyrin ( H2TPP). The results show that anharmonic effects are important when calculating k̲ _IC for transitions between electronic states that are energetically separated (Δ E) by more than 20 000–25 000 cm ⁻¹. Anharmonic effects are also important when Δ E < 20 000–25 000 cm ⁻¹ and when the accepting modes are X–H stretching vibrations with a frequency larger than 2000 cm ⁻¹. The calculations show that there is mixing between the S ₁ and S ₂ states of naphthalene induced by non-adiabatic interactions. The non-adiabatic interaction matrix element between the S ₁ and S ₂ states is 250 cm ⁻¹ and 50 cm ⁻¹ for the normal and fully deuterated naphthalene structure and this difference significantly affects the estimated fluorescence quantum yield. Besides aromatic hydrocarbons H2P and H2TPP, the k̲ _IC rate constant is also calculated for pyrometene (PM567) and tetraoxa[8]circulene (4B) with a detailed analysis of the effect of the vibrational anharmonicity.

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Article: not found

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density

Chengteh Lee, Weitao Yang, Robert Parr (1988)

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Record: found
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Article: not found

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.

Florian Weigend, Reinhart Ahlrichs (2005)

Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, density functional theory and correlated methods, for which we had chosen Møller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.