Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range
We report absolute high-resolution vacuum ultraviolet (VUV) photoabsorption cross-sections of carbon tetrachloride (CCl<sub>4</sub>) in the photon energy range 5.0–10.8 eV (248–115 nm). The molecular spectrum and electronic structure have been comprehensively investigated together with q...
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2024-11-01
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| author | Luiz V. S. Dalagnol Sarvesh Kumar Alessandra S. Barbosa Umma S. Akther Nykola C. Jones Søren V. Hoffmann Márcio H. F. Bettega Paulo Limão-Vieira |
| author_facet | Luiz V. S. Dalagnol Sarvesh Kumar Alessandra S. Barbosa Umma S. Akther Nykola C. Jones Søren V. Hoffmann Márcio H. F. Bettega Paulo Limão-Vieira |
| author_sort | Luiz V. S. Dalagnol |
| collection | DOAJ |
| description | We report absolute high-resolution vacuum ultraviolet (VUV) photoabsorption cross-sections of carbon tetrachloride (CCl<sub>4</sub>) in the photon energy range 5.0–10.8 eV (248–115 nm). The molecular spectrum and electronic structure have been comprehensively investigated together with quantum chemical calculations, providing geometries, bond lengths, vertical excitation energies and oscillator strengths. The major electronic excitations have been assigned to valence and Rydberg transitions which are also accompanied by vibrational excitation assigned to degenerate stretching, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>3</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula> and degenerate deformation <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>4</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula> modes. The rather complex nuclear dynamics along the degenerate deformation mode, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>4</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula>, have been thoroughly investigated by Time-Dependent Density Functional Theory (TD-DFT) method. The relevant Jahn–Teller distortion operative within the lowest-lying electronic excited-state is shown here for the first time in order to yield a weak absorption feature at 6.156 eV. Further calculations on the potential energy curves for the singlet excited-states along the C–Cl stretching coordinate show the relevance of efficient C–Cl bond excision. |
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| spelling | doaj-art-0dbee3d410944ca6a49a04fa38f4f23e2024-12-13T16:28:29ZengMDPI AGMolecules1420-30492024-11-012923561910.3390/molecules29235619Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy RangeLuiz V. S. Dalagnol0Sarvesh Kumar1Alessandra S. Barbosa2Umma S. Akther3Nykola C. Jones4Søren V. Hoffmann5Márcio H. F. Bettega6Paulo Limão-Vieira7Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, Curitiba 81531-980, Paraná, BrazilAtomic and Molecular Collisions Laboratory, CEFITEC-Centre of Physics and Technological Research, Department of Physics, NOVA School of Science and Technology, Universidade NOVA de Lisboa, 2829-516 Caparica, PortugalDepartamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, Curitiba 81531-980, Paraná, BrazilAtomic and Molecular Collisions Laboratory, CEFITEC-Centre of Physics and Technological Research, Department of Physics, NOVA School of Science and Technology, Universidade NOVA de Lisboa, 2829-516 Caparica, PortugalISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus, DenmarkISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus, DenmarkDepartamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, Curitiba 81531-980, Paraná, BrazilAtomic and Molecular Collisions Laboratory, CEFITEC-Centre of Physics and Technological Research, Department of Physics, NOVA School of Science and Technology, Universidade NOVA de Lisboa, 2829-516 Caparica, PortugalWe report absolute high-resolution vacuum ultraviolet (VUV) photoabsorption cross-sections of carbon tetrachloride (CCl<sub>4</sub>) in the photon energy range 5.0–10.8 eV (248–115 nm). The molecular spectrum and electronic structure have been comprehensively investigated together with quantum chemical calculations, providing geometries, bond lengths, vertical excitation energies and oscillator strengths. The major electronic excitations have been assigned to valence and Rydberg transitions which are also accompanied by vibrational excitation assigned to degenerate stretching, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>3</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula> and degenerate deformation <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>4</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula> modes. The rather complex nuclear dynamics along the degenerate deformation mode, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>v</mi></mrow><mrow><mn>4</mn></mrow><mrow><mo>′</mo></mrow></msubsup><mfenced separators="|"><mrow><msub><mrow><mi>t</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow></mfenced></mrow></semantics></math></inline-formula>, have been thoroughly investigated by Time-Dependent Density Functional Theory (TD-DFT) method. The relevant Jahn–Teller distortion operative within the lowest-lying electronic excited-state is shown here for the first time in order to yield a weak absorption feature at 6.156 eV. Further calculations on the potential energy curves for the singlet excited-states along the C–Cl stretching coordinate show the relevance of efficient C–Cl bond excision.https://www.mdpi.com/1420-3049/29/23/5619carbon tetrachloridecross-sectionstheoretical calculationsspectroscopy |
| spellingShingle | Luiz V. S. Dalagnol Sarvesh Kumar Alessandra S. Barbosa Umma S. Akther Nykola C. Jones Søren V. Hoffmann Márcio H. F. Bettega Paulo Limão-Vieira Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range Molecules carbon tetrachloride cross-sections theoretical calculations spectroscopy |
| title | Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range |
| title_full | Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range |
| title_fullStr | Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range |
| title_full_unstemmed | Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range |
| title_short | Symmetry Breaking in the Lowest-Lying Excited-State of CCl<sub>4</sub>: Valence Shell Spectroscopy in the 5.0–10.8 eV Photon Energy Range |
| title_sort | symmetry breaking in the lowest lying excited state of ccl sub 4 sub valence shell spectroscopy in the 5 0 10 8 ev photon energy range |
| topic | carbon tetrachloride cross-sections theoretical calculations spectroscopy |
| url | https://www.mdpi.com/1420-3049/29/23/5619 |
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