Excited State Absorption: Reference Oscillator Strengths, Wavefunction and TD-DFT Benchmarks

TL;DR

This paper provides a benchmark dataset of excited-state absorption oscillator strengths for small molecules, evaluating the accuracy of various computational methods including TD-DFT and wavefunction approaches.

Contribution

It introduces a comprehensive dataset of reference ESA oscillator strengths and assesses the performance of multiple computational methods against these benchmarks.

Findings

QR-TDDFT with CAM-B3LYP shows acceptable accuracy for ESA.

d-aug-cc-pVTZ basis set is consistently reliable.

ISR-ADC(3) performs exceptionally well in predicting ESA oscillator strengths.

Abstract

Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to interpret time-resolved experiments. In this contribution, we present a dataset of 53 ESA oscillator strengths in three different gauges and the associated vertical transition energies between 71 excited states of 23 small- and medium-sized molecules from the QUEST database. The reference values were obtained within the quadratic-response (QR) CC3 formalism using eight different Dunning basis sets. We found that the d-aug-cc-pVTZ basis set is always adequate while its more compact double-$\zeta$ counterpart, d-aug-cc-pVDZ, performs well in most applications. These QR-CC3 data allow us to assess the performance of QR-TDDFT, with and without applying the Tamm-Dancoff approximation, using a panel of global and range-separated hybrids (B3LYP, BH{\&}HLYP, CAM-B3LYP, LC-BLYP33, and LC-BLYP47), as well as several lower-order wavefunction methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), and ISR-ADC(3). We show that QR-TDDFT delivers acceptable errors for ESA oscillator strengths, with CAM-B3LYP showing particular promise, especially for the largest molecules of our set. We also find that ISR-ADC(3) exhibits excellent performance