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Accurate X-ray Absorption Spectra near L- and M-Edges from Relativistic Four-Component Damped Response Time-Dependent Density Functional Theory.

ABSTRACT: The simulation of X-ray absorption spectra requires both scalar and spin-orbit (SO) relativistic effects to be taken into account, particularly near L- and M-edges where the SO splitting of core p and d orbitals dominates. Four-component Dirac-Coulomb Hamiltonian-based linear damped response time-dependent density functional theory (4c-DR-TDDFT) calculates spectra directly for a selected frequency region while including the relativistic effects variationally, making the method well suited for X-ray applications. In this work, we show that accurate X-ray absorption spectra near L_2,3- and M_4,5-edges of closed-shell transition metal and actinide compounds with different central atoms, ligands, and oxidation states can be obtained by means of 4c-DR-TDDFT. While the main absorption lines do not change noticeably with the basis set and geometry, the exchange-correlation functional has a strong influence with hybrid functionals performing the best. The energy shift compared to the experiment is shown to depend linearly on the amount of Hartee-Fock exchange with the optimal value being 60% for spectral regions above 1000 eV, providing relative errors below 0.2% and 2% for edge energies and SO splittings, respectively. Finally, the methodology calibrated in this work is used to reproduce the experimental L_2,3-edge X-ray absorption spectra of [RuCl₂(DMSO)₂(Im)₂] and [WCl₄(PMePh₂)₂], and resolve the broad bands into separated lines, allowing an interpretation based on ligand field theory and double point groups. These results support 4c-DR-TDDFT as a reliable method for calculating and analyzing X-ray absorption spectra of chemically interesting systems, advance the accuracy of state-of-the art relativistic DFT approaches, and provide a reference for benchmarking more approximate techniques.

SUBMITTER: Konecny L

PROVIDER: S-EPMC8767545 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In recent decades, the scientific study of consciousness has significantly increased our understanding of this elusive phenomenon. Yet, despite critical development in our understanding of the functional side of consciousness, we still lack a fundamental theory regarding its phenomenal aspect. There is an "explanatory gap" between our scientific knowledge of functional consciousness and its "subjective," phenomenal aspects, referred to as the "hard problem" of consciousness. The phenomenal aspect of consciousness is the first-person answer to "what it's like" question, and it has thus far proved recalcitrant to direct scientific investigation. Naturalistic dualists argue that it is composed of a primitive, private, non-reductive element of reality that is independent from the functional and physical aspects of consciousness. Illusionists, on the other hand, argue that it is merely a cognitive illusion, and that all that exists are ultimately physical, non-phenomenal properties. We contend that both the dualist and illusionist positions are flawed because they tacitly assume consciousness to be an absolute property that doesn't depend on the observer. We develop a conceptual and a mathematical argument for a relativistic theory of consciousness in which a system either has or doesn't have phenomenal consciousness with respect to some observer. Phenomenal consciousness is neither private nor delusional, just relativistic. In the frame of reference of the cognitive system, it will be observable (first-person perspective) and in other frame of reference it will not (third-person perspective). These two cognitive frames of reference are both correct, just as in the case of an observer that claims to be at rest while another will claim that the observer has constant velocity. Given that consciousness is a relativistic phenomenon, neither observer position can be privileged, as they both describe the same underlying reality. Based on relativistic phenomena in physics we developed a mathematical formalization for consciousness which bridges the explanatory gap and dissolves the hard problem. Given that the first-person cognitive frame of reference also offers legitimate observations on consciousness, we conclude by arguing that philosophers can usefully contribute to the science of consciousness by collaborating with neuroscientists to explore the neural basis of phenomenal structures.

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Accurate X-ray Absorption Spectra near L- and M-Edges from Relativistic Four-Component Damped Response Time-Dependent Density Functional Theory.

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