Scientific article
English

The Challenge of Accurate Computation of Two-Photon Absorption Properties of Organic Chromophores in the Condensed Phase

Published inJournal of chemical theory and computation, vol. 17, no. 6, p. 3652-3665
Publication date2021-05-04
First online date2021-05-04
Abstract

Two strategies are applied to evaluate the effect of the environment on the two-photon absorption (TPA) cross sections for two characteristic excited states of C2H4 upon complexation with H2O. The supermolecular strategy provides the reference complexation-induced shifts and uses either the EOM-CCSD or ADC(2) method. The embedding strategy is based on frozen-density-embedding theory (FDET) and uses only fundamental constants. The TPA cross sections from high-level supermolecular calculations are extremely basis-set-sensitive. Literature data and the present study indicate that accuracy of the absolute TPA cross sections below 100 atomic units and their shifts below 10 atomic units remains a challenge. The obtained FDET results show a similar basis-set behavior. For the largest basis set (d-aug-cc-pVQZ), TPA cross sections obtained from these two strategies are in excellent agreement. The complexation-induced shifts have the correct sign of the effect and a small (12–33%) relative error in magnitude. The deviations of the FDET-derived shifts from the reference are of similar magnitude as the reliability threshold of the reference shifts.

Keywords
  • Approximation
  • Basis sets
  • Chromophores
  • Embedding
  • Energy
Citation (ISO format)
FU, Mingxue, WESOLOWSKI, Tomasz Adam. The Challenge of Accurate Computation of Two-Photon Absorption Properties of Organic Chromophores in the Condensed Phase. In: Journal of chemical theory and computation, 2021, vol. 17, n° 6, p. 3652–3665. doi: 10.1021/acs.jctc.1c00204
Main files (1)
Article (Published version)
accessLevelRestricted
Identifiers
Additional URL for this publicationhttps://pubs.acs.org/doi/10.1021/acs.jctc.1c00204
Journal ISSN1549-9618
48views
0downloads

Technical informations

Creation23/09/2024 13:16:46
First validation23/09/2024 14:04:51
Update23/09/2024 14:04:51
Status update23/09/2024 14:04:51
Last indexation10/06/2025 21:57:29
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack