Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances

Cole R Sagan; Cate S Anstöter; Mushir Thodika; Kenneth D Wilson; Spiridoula Matsika; Etienne Garand

doi:10.1021/acs.jpclett.2c02931

Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances

Cole R Sagan, Cate S Anstöter, Mushir Thodika, Kenneth D Wilson, Spiridoula Matsika, Etienne Garand

Research output: Contribution to journal › Article › peer-review

Abstract

The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm -1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.

Original language	English
Pages (from-to)	10245-10252
Number of pages	8
Journal	JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume	13
Issue number	44
Early online date	27 Oct 2022
DOIs	https://doi.org/10.1021/acs.jpclett.2c02931
Publication status	Published - 10 Nov 2022

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10.1021/acs.jpclett.2c02931

Cite this

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title = "Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances",

abstract = "The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm -1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules. ",

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T1 - Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances

AU - Sagan, Cole R

AU - Anstöter, Cate S

AU - Thodika, Mushir

AU - Wilson, Kenneth D

AU - Matsika, Spiridoula

AU - Garand, Etienne

PY - 2022/11/10

Y1 - 2022/11/10

N2 - The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm -1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.

AB - The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm -1 line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.

U2 - 10.1021/acs.jpclett.2c02931

DO - 10.1021/acs.jpclett.2c02931

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