Excited states of diphenylacetylene (tolan): Near and vacuum UV polarization spectroscopy

Duy Duc Nguyen; Nykola C. Jones; Søren Vrønning Hoffmann; Jens Spanget-Larsen

doi:10.5155/eurjchem.15.2.87-92.2546

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Published: Jun 30, 2024

DOI: https://doi.org/10.5155/eurjchem.15.2.87-92.2546

Keywords:

MCD B-terms, Near and vacuum UV, Synchrotron radiation, Stretched polyethylene, Polarization spectroscopy, LCOAO and TD-DFT calculations

Section

Research Article

Issue

Vol. 15 No. 2 (2024): June 2024

Dates

Received 2024-03-09
Accepted 2024-04-04
Published 2024-06-30

Duy Duc Nguyen

Department of Science and Environment, Roskilde University, Universitetsvej 1, DK-4000 Roskilde, Denmark

https://orcid.org/0009-0002-4241-8256

Nykola C. Jones

Centre for Storage Ring Facilities (ISA), Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C, Denmark

https://orcid.org/0000-0002-4081-6405

Søren Vrønning Hoffmann

Centre for Storage Ring Facilities (ISA), Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C, Denmark

https://orcid.org/0000-0002-8018-5433

Jens Spanget-Larsen

Department of Science and Environment, Roskilde University, Universitetsvej 1, DK-4000 Roskilde, Denmark

https://orcid.org/0000-0002-4212-7603

Abstract

The UV absorbance spectrum of the important chromophore diphenylacetylene (tolan) is investigated by Synchrotron Radiation Linear Dichroism (SRLD) spectroscopy using stretched polyethylene as an anisotropic solvent. The investigation covers the range of 58,000-28,000 cm^–1 (172-360 nm). The observed linear dichroism provides information on the transition moment directions of the four main absorbance bands A, B, C, and D at 33,300, 44,400, 51,000, and 57,000 cm^-1(300, 225, 196, and 175 nm). The experimental wavenumbers, intensities, and polarization directions are compared with the results of quantum chemical calculations using the semiempirical all-valence-electrons method Linear Combination of Orthogonalized Atomic Orbitals (LCOAO) and Time-Dependent Density Functional Theory (TD-DFT) with the functional CAM-B3LYP. Magnetic Circular Dichroism (MCD) B-terms predicted with LCOAO suggest that a number of optically weak transitions may be observed by MCD spectroscopy.

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Nguyen, D. D.; Jones, N. C.; Hoffmann, S. V.; Spanget-Larsen, J. Excited States of Diphenylacetylene (tolan): Near and Vacuum UV Polarization Spectroscopy. Eur. J. Chem. 2024, 15, 87-92.

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