Stabilization Method as a Tool for Electronic State Spectroscopy

Randi, Pedro A. S.; Limão-Vieira, Paulo; Bettega, Márcio H.F.

http://hdl.handle.net/10362/187009

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Autores

Randi, Pedro A. S.

Limão-Vieira, Paulo

Bettega, Márcio H.F.

Resumo(s)

We propose a new systematic approach to distinguish valence and diffuse electronically excited states of polyatomic molecules. This method applies the stabilization technique of Hazi and Taylor [Phys. Rev. A 1970, 1 (1109)] to neutral excited states, using basis set diffuseness as the stabilization parameter. By monitoring how excited states behave under basis set contraction, one can differentiate valence states from Rydberg and mixed valence-Rydberg states, reducing the arbitrariness of previous strategies. Valence states remain stable, whereas the energies of Rydberg and mixed states vary. This approach is compatible with any electronic structure method. To illustrate its applicability, we characterize the singlet excited states of CCl4, HCOOH, and 2-chlorotoluene. This provides a valuable tool for investigating the nature of the electronically excited states.

Descrição

Funding Information: The Article Processing Charge for the publication of this research was funded by the Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES), Brazil (ROR identifier: 00x0ma614). PASR and MHFB acknowledge support from the Brazilian agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). PASR and MHFB also acknowledge Prof. Carlos de Carvalho for computational support at LFTC-DFis-UFPR and at LCPAD-UFPR. PLV acknowledges the Portuguese National Funding Agency (FCT) through research grant CEFITEC (UIDB/00068/2020) and his visiting professor position at Federal University of Paraná, Curitiba, Brazil. Finally, PASR would like to acknowledge the meaningful discussions with Dr. Fábris Kossoski and MSc. Luiz Vitorino dos Santos Dalagnol that set into motion the ideas presented in the work. Publisher Copyright: © 2025 The Authors. Published by American Chemical Society.