Density functional theory calculations of the non-resonant and resonant X-ray emission spectroscopy of carbon fullerenes and nanotubes

Hanson‐Heine, Magnus W. D.; George, Michael W.; Besley, Nicholas A.

doi:10.1016/j.cplett.2018.02.028

Cited by 10 publications

(19 citation statements)

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“…This is illustrated by the study of carbon nanostructures including fullerenes and carbon nanotubes. 43 Figure 5 shows the computed and experimental non-resonant X-ray emission spectra for shown the spectra are insensitive to factors such as nanotube diameter, length and chirality. 43 More recently, our work has shown how XES can be determined using TDDFT through the use of a reference determinant with a core-hole.…”

Section: X-ray Emission Spectroscopy (Xes)mentioning

confidence: 99%

“…43 Figure 5 shows the computed and experimental non-resonant X-ray emission spectra for shown the spectra are insensitive to factors such as nanotube diameter, length and chirality. 43 More recently, our work has shown how XES can be determined using TDDFT through the use of a reference determinant with a core-hole. 44 The advantage of this approach is that the core-hole relaxation is included and all the emission transitions can be captured in a single calculation.…”

Section: X-ray Emission Spectroscopy (Xes)mentioning

confidence: 99%

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Density Functional Theory Based Methods for the Calculation of X-ray Spectroscopy

Besley

2020

Acc. Chem. Res.

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108

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Conspectus The availability of new light sources combined with the realization of the unique capabilities of spectroscopy in the X-ray region has driven tremendous advances in the field of X-ray spectroscopy. Currently, these techniques are emerging as powerful analytical tools for the study of a wide range of problems encompassing liquids, materials, and biological systems. Time-resolved measurements add a further dimension to X-ray spectroscopy, opening up the potential to resolve ultrafast chemical processes at an atomic level. X-ray spectroscopy encompasses a range of techniques which provide complementary information, and these include X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), and resonant inelastic X-ray scattering (RIXS). In many studies, the interpretation of the experimental data relies upon calculations to enable the nature of the underlying molecular structure, electronic structure, and bonding to be revealed. Density functional theory (DFT) based methods are some of the most widely used methods for the simulation of X-ray spectra. In this Account, we focus on our recent contributions to the simulation of a range of X-ray spectroscopic techniques using DFT and linear-response time-dependent density functional theory (TDDFT) and show how these methods can provide a computational toolkit for the simulation of X-ray spectroscopy. The importance of the exchange-correlation functional for the calculation of XAS is discussed, and the introduction of short-range corrected functionals is described. The application of these calculations to study large systems through the use of efficient implementations of TDDFT will be highlighted, with the use of these methods illustrated through studies of ionic liquids and transition metal complexes. The extension of TDDFT to calculate XES through the use of a reference determinant for the core-ionized state will be described, and the factors that affect the accuracy of the computed spectra discussed. The application of these approaches will be illustrated through the study of a range of organic molecules and transition metal complexes, which also show how going beyond the dipole approximation in determining the transition intensities can be critical. The application of these approaches to the simulation of the RIXS spectrum of water will also be described, highlighting how ultrafast dynamics on the femtoscale time scale are evident in the measured spectra. In these calculations, the description of the core-ionized and core-excited states becomes increasingly important, and the role of the basis set in accurately describing these states will be explored.

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Section: X-ray Emission Spectroscopy (Xes)mentioning

confidence: 99%

Section: X-ray Emission Spectroscopy (Xes)mentioning

confidence: 99%

Density Functional Theory Based Methods for the Calculation of X-ray Spectroscopy

Besley

2020

Acc. Chem. Res.

Self Cite

108

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“…This is similar in spirit to Koopmans' theorem for XPS, and the advantages of this approach are that it only requires a Kohn–Sham DFT calculation to be performed and it is able to predict the relative energies of the experimental bands to a high level of accuracy that allow observed experimental bands to be assigned with confidence. This method has been used successfully 165,166 and allows the XES of large systems such as carbon nanotubes to be studied 167 …”

Section: X‐ray Emission Spectroscopymentioning

confidence: 99%

“…One computational approach to interpreting RIXS maps is to treat the problem in terms of resonant X‐ray emission (RXES). In this approach, X‐ray emission spectra are computed for different core‐excited states 22,166,167,208‐213 . This can be achieved using TDDFT by using a reference determinant corresponding to the relevant core‐excited state 214 .…”

Section: Other X‐ray Spectroscopic Techniquesmentioning

confidence: 99%

“…This method has been used successfully 165,166 and allows the XES of large systems such as carbon nanotubes to be studied. 167 Going beyond this approach requires some explicit consideration of the core-ionized state and the associated relaxation of the electronic density. This can be achieved via ΔSCF calculations, however converging SCF calculations for the large number of final states is challenging.…”

Section: X-ray Emission Spectroscopymentioning

confidence: 99%

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Modeling of the spectroscopy of core electrons with density functional theory

Besley

2021

WIREs Comput Mol Sci

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100

104

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The availability of X‐ray light sources with increased resolution and intensity has provided a foundation for increasingly sophisticated experimental studies exploiting the spectroscopy of core electrons to probe fundamental chemical, physical, and biological processes. Quantum chemical calculations can play a critical role in the analysis of these experimental measurements. The relatively low computational cost of density functional theory (DFT) and time‐dependent density functional theory (TDDFT) make them attractive choices for simulating the spectroscopy of core electrons. An overview of current developments to apply DFT and TDDFT to study the key techniques of X‐ray photoelectron spectroscopy, X‐ray absorption spectroscopy, X‐ray emission spectroscopy, and resonant inelastic X‐ray scattering is presented. Insight into the accuracy that can be achieved, in conjunction with an examination of the limitations and challenges to modeling the spectroscopy of core electrons with DFT is provided. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy Electronic Structure Theory > Density Functional Theory

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Time-dependent density functional theory study of the X-ray emission spectroscopy of amino acids and proteins

Foerster

Besley

2020

Chemical Physics Letters

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Density functional theory calculations of the non-resonant and resonant X-ray emission spectroscopy of carbon fullerenes and nanotubes

Cited by 10 publications

References 50 publications

Density Functional Theory Based Methods for the Calculation of X-ray Spectroscopy

Density Functional Theory Based Methods for the Calculation of X-ray Spectroscopy

Modeling of the spectroscopy of core electrons with density functional theory

Time-dependent density functional theory study of the X-ray emission spectroscopy of amino acids and proteins

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