Simulating core electron binding energies of halogenated species adsorbed on ice surfaces and in solution <i>via</i> relativistic quantum embedding calculations

A., Opoku, Richard; Toubin, Céline; Gomes, André Severo Pereira

doi:10.1039/d1cp05836c

Cited by 6 publications

(6 citation statements)

References 110 publications

(254 reference statements)

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“…As discussed by Gomes et al, the physical process behind these changes is that the effect of the crystal environment lowers the energies of both occupied and virtual orbitals by roughly the same amounts. In addition to that, the energies of occupied valence ,, and core levels are shifted by essentially the same amount as by the environment. With that, relative measures such as excitation energies turn out to be weakly affected by the environment.…”

Section: Resultsmentioning

confidence: 98%

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Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Misael

Gomes

2023

Inorg. Chem.

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X-ray spectroscopies, by their high selectivity and sensitivity to the chemical environment around the atoms probed, provide significant insights into the electronic structures of molecules and materials. Interpreting experimental results requires reliable theoretical models, accounting for environmental, relativistic, electron correlation, and orbital relaxation effects in a balanced manner. In this work, we present a protocol for the simulation of core excited spectra with damped response timedependent density functional theory based on the Dirac−Coulomb Hamiltonian (4c-DR-TD-DFT), in which environmental effects are accounted for through the frozen density embedding (FDE) method. We showcase this approach for the uranium M 4 -and L 3edges and oxygen K-edge of the uranyl tetrachloride (UO 2 Cl 4 2− ) unit as found in a host Cs 2 UO 2 Cl 4 crystal. We have found that the 4c-DR-TD-DFT simulations yield excitation spectra that very closely match the experiment for the uranium M 4 -edge and the oxygen K-edge, with good agreement for the broad experimental spectra for the L 3 -edge. By decomposing the complex polarizability in terms of its components, we have been able to correlate our results with angle-resolved spectra. We have observed that for all edges, but in particular the uranium M 4 -edge, an embedded model in which the chloride ligands are replaced by an embedding potential reproduces rather well the spectral profile obtained for UO 2 Cl 4 2− . Our results underscore the importance of the equatorial ligands to simulating core spectra at both uranium and oxygen edges.

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Section: Resultsmentioning

confidence: 98%

“…For ionizations, on the other hand, long-range interactions with the environment are important ,, and require the use of more sophisticated structural models. We shall address the ionizations of uranyl in Cs 2 UO 2 Cl 4 in a separate publication.…”

Section: Resultsmentioning

confidence: 99%

Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Misael

Gomes

2023

Inorg. Chem.

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“…204 Finally, we note that as another example, a study on the X-ray photoelectron spectrum of hydrogen chloride and chloride ions on ice surfaces or in water droplets based on FDE combined with relativistic core-valence separation equation-of-motion coupled cluster theory was presented by Gomes and co-workers. 205…”

Section: Impurities and Adsorbed Moleculesmentioning

confidence: 99%

Subsystem density‐functional theory (update)

Jacob,

Neugebauer

2024

WIREs Comput Mol Sci

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The past years since the publication of our review on subsystem density‐functional theory (sDFT) (WIREs Comput Mol Sci. 2014, 4:325–362) have witnessed a rapid development and diversification of quantum mechanical fragmentation and embedding approaches related to sDFT and frozen‐density embedding (FDE). In this follow‐up article, we provide an update addressing formal and algorithmic work on sDFT/FDE, novel approximations developed for treating the non‐additive kinetic energy in these DFT/DFT hybrid methods, new areas of application and extensions to properties previously not accessible, projection‐based techniques as an alternative to solely density‐based embedding, progress in wavefunction‐in‐DFT embedding, new fragmentation strategies in the context of DFT which are technically or conceptually similar to sDFT, and the blurring boundary between advanced DFT/MM and approximate DFT/DFT embedding methods.This article is categorized under: Electronic Structure Theory > Density Functional Theory

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“…In non-relativistic calculations, our EOM results closely match the TPA results derived from QR-CC in DALTON, with only about a 3% discrepancy, in line with the discrepancies observed for the hyperpolarizabilties. 107 From the first three columns, it becomes apparent that when using standard selection schemes, we cannot achieve reasonable TPA values in comparison to the original canonical orbital results, even with a threshold of 1.0d −6 for the occupation number where we retrieve more than 99.99% correlation energy for the ground state. We find the excitation energy of the TPA target state (4s5s) 1 S 0 is markedly overestimated in FNO calculations, especially when using threshold of 1.0d −4 and 1.0d −5 .…”

Section: Two-photon Absorption Cross-sectionsmentioning

confidence: 92%

“…In any case, it is clear that once we complete the extension of the current code to use the ExaTENSOR library, which is suited for distributed memory computing architectures, we will significantly widen the range of applications both EOM and response theory codes can handle. For example, prior work in our group evaluated the effect of the environment (solvent, etc) on the ionization energy of valence [106] and core electrons [107] of the halide ions by comb-5.5. EOM-CCSD IP and EA sigma vectors were not given in SI of Chapter 3151 ing the relativistic EOM-IP and frozen density embedding (FDE) methods [108][109][110].…”

Section: Perspectivesmentioning

confidence: 99%

Molecular properties in the linear response regime and beyond with relativistic coupled-cluster

Yuan

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This thesis mainly focuses on the development and implementation of new methods to study various types of response properties for molecules containing heavy elements. We implement static and frequency-dependent linear and quadratic response properties based upon relativistic coupled cluster wave function models. The validations are done by calculating various types of molecular properties such as frequency- (in)dependent (hyper)polarizability (purely electric), indirect spin-spin coupling constant (purely magnetic), and optical rotation (mixed electric-magnetic). Moreover, the current implementations also allow evaluation of the absorption cross-sections: the linear response code can evaluate the damped response functions, which can be used to calculate the one-photon absorption cross-sections, and the quadratic response code can evaluate the two-photon absorption cross-sections provided the wave functions of the target states exist. In addition, we also implement the equation-of-motion (EOM) coupled-cluster theory to evaluate the ionization potential, electron affinity, and excitation energy. The new EOM codes reproduce the results from the previous implementation in the program RELCCSD very well. All the codes are implemented on the new GPU-accelerated coupled cluster module Ex- aCorr in DIRAC. This module is designed for dealing with large systems and perform- ing efficiently coupled cluster calculations on modern supercomputer architectures. To further reduce the calculation cost, we implement the relativistic MP2 frozen natural orbitals (FNOs) to reduce the virtual orbital space in the correlated calculation. The pilot tests show with using FNOs, one can obtain reliable estimates for both energies and molecular properties with only half the size of the full spaces. Apart from the development work, this thesis also contains applications of the existing relativistic quantum chemistry models to obtain the highly accurate electronic structures and transition properties of molecules containing heavy elements. We discuss the importance of the evaluation of the relativistic effect and electron correlation on an equal footing and the corresponding impact on different topics such as molecular laser cooling and plasma physics.

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Simulating core electron binding energies of halogenated species adsorbed on ice surfaces and in solution via relativistic quantum embedding calculations

Abstract: In this work we investigate the effects of the environment on the X-ray photoelectron spectra of hydrogen chloride and the chloride ions adsorbed on ice surfaces, as well as of...

Cited by 6 publications

References 110 publications

Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Subsystem density‐functional theory (update)

Molecular properties in the linear response regime and beyond with relativistic coupled-cluster

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Simulating core electron binding energies of halogenated species adsorbed on ice surfaces and in solution via relativistic quantum embedding calculations

Abstract: In this work we investigate the effects of the environment on the X-ray photoelectron spectra of hydrogen chloride and the chloride ions adsorbed on ice surfaces, as well as of...

Cited by 6 publications

References 110 publications

Core Excitations of Uranyl in Cs2UO2Cl4 from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Core Excitations of Uranyl in Cs2UO2Cl4 from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Subsystem density‐functional theory (update)

Molecular properties in the linear response regime and beyond with relativistic coupled-cluster

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Product

Resources

About

Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Core Excitations of Uranyl in Cs₂UO₂Cl₄ from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations