Comment on: “Toward Accurate Two-Photon Absorption Spectrum Simulations: Exploring the Landscape beyond the Generalized Gradient Approximation”

Grotjahn, Robin; Furche, Filipp

doi:10.1021/acs.jpclett.4c00650

Cited by 2 publications

References 47 publications

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Two-Photon Absorption Strengths of Small Molecules: Reference CC3 Values and Benchmarks

Naim,

Zaleśny,

Jacquemin

2024

J. Chem. Theory Comput.

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We present a large dataset of highly accurate two-photon transition strengths (δ TPA ) determined for standard small molecules. Our reference values have been calculated using the quadratic response implementation of the thirdorder coupled cluster method including iterative triples (Q-CC3). The aug-cc-pVTZ atomic basis set is used for molecules with up to five non-hydrogen atoms, while larger molecules are assessed with aug-cc-pVDZ; the differences due to the basis sets are discussed. This dataset, encompassing 82 singlet transitions of various characters (Rydberg, valence, and double excitations), enables a comprehensive benchmark of smaller basis sets and alternative wavefunction methods when Q-CC3 calculations become beyond reach as well as timedependent density functional theory (TD-DFT) approaches. The evaluated wavefunction methods include quadratic response and equation-of-motion CCSD approximations, Q-CC2, and second-order algebraic diagrammatic construction in its intermediate state representation (I-ADC2). In the TD-DFT framework, a set of five commonly used exchange−correlation functionals are evaluted. This extensive analysis provides a quantitative assessment of these methods, revealing how different system sizes, response intensities, and types of transitions affect their performances.

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