When a system has evolved far from a ground-state, the adiabatic approximations commonly used in time-dependent density functional theory calculations completely fail in some applications, while giving qualitatively good predictions in others, and sometimes even quantitative predictions. It is not clearly understood why this is so, and developing practical approximations going beyond the adiabatic approximation remains a challenge. This paper explores three different lines of investigation. First, an expression for the exact time-dependent exchange-correlation potential suggests that the accuracy of an adiabatic approximation is intimately related to the deviation between the natural orbital occupation numbers of the physical system and those of the Kohn-Sham system, and we explore this on some exactly-solvable model systems. The exact expression further suggests a path to go beyond the adiabatic approximations, and in the second part we discuss a newly proposed class of memory-dependent approximations developed in this way. Finally, we derive a new expression for the exact exchange-correlation potential from a coupling-constant path integration.
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http://dx.doi.org/10.1039/d0fd00049c | DOI Listing |
J Phys Chem A
January 2025
Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, D-81377 Munich, Germany.
Recently, we investigated a number of so-called σ- and τ-functionals based on the adiabatic-connection fluctuation-dissipation theorem (ACFDT); particularly, extensions of the random phase approximation (RPA) with inclusion of an exchange kernel in the form of an antisymmetrized Hartree kernel. One of these functionals, based upon the approximate exchange kernel (AXK) of Bates and Furche, leads to a nonlinear contribution of the spline function used within σ-functionals, which we previously avoided through the introduction of a simplified "top-down" approach in which the σ-functional modification is inserted a posteriori following the analytic coupling strength integration within the framework of the ACFDT and which was shown to provide excellent performance for the GMTKN55 database when using hybrid PBE0 reference orbitals. In this work, we examine the analytic "bottom-up" approach in which the spline function is inserted a priori, i.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
We revisit the naked transition metal cation (Ti) and methanol reaction and go beyond the standard Landau-Zener (LZ) picture when modeling the intersystem crossing (ISC) rate between the lowest doublet and quartet states. We use both (i) unconstrained Born-Oppenheimer molecular dynamics (BOMD) calculations with an approximate two-state method to estimate population transfer between spin diabats and (ii) constrained dynamics to explore energetically accessible portions of the - 1 crossing seam, where is the total number of internal degrees of freedom. Whereas previous LZ calculations (that necessarily relied on the Condon approximation to be valid) fell short and predicted much slower crossing probabilities than shown in experiment, we show that ISC can occur rapidly because the spin-orbit coupling (SOC) between the doublet and quartet surfaces can vary by 2 orders of magnitude (depending on where in the seam the crossing occurs during dynamics) and the crossing region is revisited multiple times during a dynamics run of a few hundred femtoseconds.
View Article and Find Full Text PDFOphthalmol Sci
October 2024
Department of Biomedical Engineering, Stevens Institute of Technology, Hoboken, New Jersey.
Objective: To investigate retinal vascular permeability mapping as a potential biomarker for diabetic retinopathy in subjects with diabetes with no signs of retinopathy and with mild nonproliferative retinopathy.
Design: This is a case-control study.
Subjects: Participants included 7 healthy controls, 22 subjects with diabetes mellitus and no clinical signs of retinopathy (DMnoDR), and 7 subjects with mild nonproliferative diabetic retinopathy (NPDR).
J Chem Theory Comput
January 2025
Department of Chemistry, Durham University, South Road, Durham DH1 3LE, U.K.
Classical reaction barriers in density-functional theory are considered from the perspective of the density-fixed adiabatic connection. A 'reaction adiabatic-connection integrand', , is introduced, where λ is the electron-electron interaction strength, for which equals the barrier, meaning the barrier can be easily visualized as the area under a plot of vs λ. For five chemical reactions, plots of reference , calculated from Lieb maximizations at the coupled-cluster level of theory, are compared with approximate , calculated from common exchange-correlation functionals using coordinate scaling, for coupled-cluster densities.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Physics and Chemistry of Materials (T-1), Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
In the present work, we studied 27 FeH and 6 FeH electronic states using multireference configuration interaction (MRCI), Davidson-corrected MRCI (MRCI+Q), and coupled cluster singles doubles and perturbative triples [CCSD(T)] wavefunction theory (WFT) calculations conjoined with large quadruple- and quintuple- quality correlation consistent basis sets. We report their potential energy curves (PEC), energy related properties, spectroscopic parameters, and spin-orbit couplings. Dipole moment curves (DMC) and transition dipole moment curves (TDMC) of several low-lying electronic states of FeH and FeH are also introduced.
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