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

R. R. Valiev, R. T. Nasibullin, V. N. Cherepanov, G. V. Baryshnikov, D. Sundholm, H. Ågren, B. F. Minaev, T. Kurtén

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

A new method for calculating internal conversion rate constants (kIC), including anharmonic effects and using the Lagrangian multiplier technique, is proposed. The deuteration effect on kIC is investigated for naphthalene, anthracene, free-base porphyrin (H2P) and tetraphenylporphyrin (H2TPP). The results show that anharmonic effects are important when calculating kIC for transitions between electronic states that are energetically separated (ΔE) by more than 20 000-25 000 cm-1. Anharmonic effects are also important when ΔE < 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 S1 and S2 states of naphthalene induced by non-adiabatic interactions. The non-adiabatic interaction matrix element between the S1 and S2 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 kIC rate constant is also calculated for pyrometene (PM567) and tetraoxa[8]circulene (4B) with a detailed analysis of the effect of the vibrational anharmonicity. This journal is

Original languageEnglish
Pages (from-to)22314-22323
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume22
Issue number39
DOIs
Publication statusPublished - 21 Oct 2020

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'First-principles calculations of anharmonic and deuteration effects on the photophysical properties of polyacenes and porphyrinoids'. Together they form a unique fingerprint.

Cite this