Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Spin-State Dependence of Exchange-Correlation Holes

<div>Applications of density functionaltheory (DFT) in computational chemistry rely on an approximate exchange-correlation (xc) functional. However, existing approximations can fail dramatically for open-shell molecules, in particular for transition-metal complexes or radicals. Most importantly, predicting energy-differences between different spin-states with approximate exchange-correlation functionals remains extremely challenging. Formally, it is known that the exact xc functional should be spin-state dependent, but none of the available approximations features such an explicit spin-state dependence [Ch.~R.~Jacob, M.~Reiher, \textit{Int. J. Quantum Chem.}, 2012, \textbf{112}, 3661–3684]. Thus, to find novel approximations for the xc functional for open-shell systems, the development of spin-state dependent xc functionals appears to be a promising avenue. Here, we set out to shed light on the spin-state dependence of the xc functional by investigating the underlying xc holes, which we extract from configuration interaction calculations for model systems. We analyze the similarities and differences between the xc holes of the lowest-energy singlet and triplet states of the dihydrogen molecule, the helium atom, and the lithium dimer. To shed further light on the spin-state dependence of these xc holes we also discuss exact conditions that can be derived from the spin structure of the reduced two-electron density matrix. Altogether, our results suggest several possible routes towards the construction of explicitly spin-state dependent approximations for the xc functional.<br></div><br>

Efficient Evaluation of Molecular Electrostatic Potential in Large Systems

An algorithm for the efficient computation of molecular electrostatic potential is reported. It is based on the partition/expansion of density into (pseudo) atomic fragments with the method of Deformed Atoms in Molecules, which allows to compute the potential as a sum of atomic contributions. These contributions are expressed as a series of irregular spherical harmonics times effective multipole moments and inverse multipole moments, including short-range terms. The problem is split into two steps. The first one consists of the partition/expansion of density accompanied by the computation of multipole moments, and its cost depends on the size of the basis set used in the computation of electron density within the Linear Combination of Atomic Orbitals framework. The second one is the actual computation of the electrostatic potential from the quantities calculated in the first step, and its cost depends on the number of computation points. For a precision in the electrostatic potential of six decimal figures, the algorithm leads to a dramatic reduction of the computation time with respect to the calculation from electron density matrix and integrals involving basis set functions.

Imaging of transition charge densities involving carbon core excitations by all X-ray sum-frequency generation

X-ray diffraction signals from the time-evolving molecular charge density induced by selective core excitation of chemically inequivalent carbon atoms are calculated. A narrowband X-ray pulse selectively excites the carbon K-edge of the –CH 3 or –CH 2 F groups in fluoroethane (CH 3 –CH 2 F). Each excitation creates a distinct core coherence which depends on the character of the electronic transition. Direct propagation of the reduced single-electron density matrix, using real-time time-dependent density functional theory, provides the time-evolving charge density following interactions with external fields. The interplay between partially filled valence molecular orbitals upon core excitation induces characteristic femtosecond charge migration which depends on the core–valence coherence, and is monitored by the sum-frequency generation diffraction signal. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays’.

Is it Reasonable to Obtain Information on the Polarizability and Hyperpolarizability Only from the Electron Density?

Formulae for the static electronic polarizability and hyperpolarizability are derived in terms of moments of the ground-state electron density matrix by applying the Unsöld approximation and a generalization of the Fermi-Amaldi approximation. The latter formula for the hyperpolarizability appears to be new. The formulae manifestly transform correctly under rotations, and they are observed to be essentially cumulant expressions. Consequently, they are additive over different regions. The properties of the formula are discussed in relation to others that have been proposed in order to clarify inconsistencies. The formulae are then tested against coupled-perturbed Hartree-Fock results for a set of 40 donor-π-acceptor systems. For the polarizability, the correlation is reasonable; therefore, electron density matrix moments from theory or experiment may be used to predict polarizabilities. By constrast, the results for the hyperpolarizabilities are poor, not even within one or two orders of magnitude. The formula for the two- and three-particle density matrices obtained as a side result in this work may be interesting for density functional theories.

Bounded weak solutions to a matrix drift–diffusion model for spin-coherent electron transport in semiconductors

The global-in-time existence and uniqueness of bounded weak solutions to a spinorial matrix drift–diffusion model for semiconductors is proved. Developing the electron density matrix in the Pauli basis, the coefficients (charge density and spin-vector density) satisfy a parabolic 4 × 4 cross-diffusion system. The key idea of the existence proof is to work with different variables: the spin-up and spin-down densities as well as the parallel and perpendicular components of the spin-vector density with respect to the precession vector. In these variables, the diffusion matrix becomes diagonal. The proofs of the L∞ estimates are based on Stampacchia truncation as well as Moser- and Alikakos-type iteration arguments. The monotonicity of the entropy (or free energy) is also proved. Numerical experiments in one-space dimension using a finite-volume discretization indicate that the entropy decays exponentially fast to the equilibrium state.