Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV
High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2017-10-01
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| Series: | Beilstein Journal of Nanotechnology |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjnano.8.220 |
| _version_ | 1830475424521519104 |
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| author | Mónica Mendes Khrystyna Regeta Filipe Ferreira da Silva Nykola C. Jones Søren Vrønning Hoffmann Gustavo García Chantal Daniel Paulo Limão-Vieira |
| author_facet | Mónica Mendes Khrystyna Regeta Filipe Ferreira da Silva Nykola C. Jones Søren Vrønning Hoffmann Gustavo García Chantal Daniel Paulo Limão-Vieira |
| author_sort | Mónica Mendes |
| collection | DOAJ |
| description | High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The higher resolution obtained reveals previously unresolved spectral features of W(CO)6. The spectrum shows two higher-energy bands (in the energy ranges of 7.22–8.12 eV and 8.15–9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin–orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO)6, a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements. |
| first_indexed | 2024-12-21T15:36:10Z |
| format | Article |
| id | doaj.art-2b7bf6acf413442f8ae9b3c9b4b1fad9 |
| institution | Directory Open Access Journal |
| issn | 2190-4286 |
| language | English |
| last_indexed | 2024-12-21T15:36:10Z |
| publishDate | 2017-10-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Nanotechnology |
| spelling | doaj.art-2b7bf6acf413442f8ae9b3c9b4b1fad92022-12-21T18:58:37ZengBeilstein-InstitutBeilstein Journal of Nanotechnology2190-42862017-10-01812208221810.3762/bjnano.8.2202190-4286-8-220Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eVMónica Mendes0Khrystyna Regeta1Filipe Ferreira da Silva2Nykola C. Jones3Søren Vrønning Hoffmann4Gustavo García5Chantal Daniel6Paulo Limão-Vieira7Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Universidade NOVA de Lisboa, 2829-516, Caparica, PortugalLaboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Universidade NOVA de Lisboa, 2829-516, Caparica, PortugalLaboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Universidade NOVA de Lisboa, 2829-516, Caparica, PortugalISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000, Aarhus C, DenmarkISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000, Aarhus C, DenmarkInstituto de Física Fundamental, Consejo Superior de Investigaciones Científicas (CSIC), Serrano 113-bis, 28006 Madrid, SpainLaboratoire de Chimie Quantique, Institut de Chimie Strasbourg, UMR7177 CNRS/Université de Strasbourg 1 Rue Blaise Pascal BP296/R8, F-67008 Strasbourg, FranceLaboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Universidade NOVA de Lisboa, 2829-516, Caparica, PortugalHigh-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The higher resolution obtained reveals previously unresolved spectral features of W(CO)6. The spectrum shows two higher-energy bands (in the energy ranges of 7.22–8.12 eV and 8.15–9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin–orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO)6, a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements.https://doi.org/10.3762/bjnano.8.220cross sectionsdensity functional theory (DFT) calculationsfocused electron beam induced deposition (FEBID)photoabsorptiontungsten hexacarbonyl |
| spellingShingle | Mónica Mendes Khrystyna Regeta Filipe Ferreira da Silva Nykola C. Jones Søren Vrønning Hoffmann Gustavo García Chantal Daniel Paulo Limão-Vieira Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV Beilstein Journal of Nanotechnology cross sections density functional theory (DFT) calculations focused electron beam induced deposition (FEBID) photoabsorption tungsten hexacarbonyl |
| title | Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV |
| title_full | Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV |
| title_fullStr | Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV |
| title_full_unstemmed | Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV |
| title_short | Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV |
| title_sort | comprehensive investigation of the electronic excitation of w co 6 by photoabsorption and theoretical analysis in the energy region from 3 9 to 10 8 ev |
| topic | cross sections density functional theory (DFT) calculations focused electron beam induced deposition (FEBID) photoabsorption tungsten hexacarbonyl |
| url | https://doi.org/10.3762/bjnano.8.220 |
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