TY - JOUR
T1 - 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
AU - Mendes, Mónica
AU - Regeta, Khrystyna
AU - da Silva, Filipe Ferreira
AU - Jones, Nykola C.
AU - Hoffmann, Søren Vrønning
AU - García, Gustavo
AU - Daniel, Chantal
AU - Limão-Vieira, Paulo
N1 - info:eu-repo/grantAgreement/FCT/5876/147412/PT#
grants PD/BD/106038/2015.
researcher position IF-FCT IF/00380/2014.
RaBBiT, PD/00193/2012); UID/Multi/ 04378/2013 (UCIBIO).
Spanish Ministerio de Economia, Industria y Competitividad (Project No. FIS2016-80440).
The Labex "Chimie des Systemes Complexes" (ANR-10-LABX-0026_CSC).
European Community's Seventh Framework Programme (FP7/2007-2013) CALIPSO under grant agreement number 312284.
EU/ESF COST Action CELINA CM1301.
PY - 2017/10/23
Y1 - 2017/10/23
N2 - 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.
AB - 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.
KW - Cross sections
KW - Density functional theory (DFT) calculations
KW - Focused electron beam induced deposition (FEBID)
KW - Photoabsorption
KW - Tungsten hexacarbonyl
UR - http://www.scopus.com/inward/record.url?scp=85032591601&partnerID=8YFLogxK
U2 - 10.3762/bjnano.8.220
DO - 10.3762/bjnano.8.220
M3 - Article
C2 - 29114447
AN - SCOPUS:85032591601
SN - 2190-4286
VL - 8
SP - 2208
EP - 2218
JO - Beilstein Journal of Nanotechnology
JF - Beilstein Journal of Nanotechnology
IS - 1
ER -