Electron pair

Abstract: Graduate-level text explains modern in-depth approaches to the calculation of the electronic structure and properties of molecules Hartree-Fock approximation, electron pair approximation, much more Largely self-contained, only prerequisite is solid course in physical chemistry Over 150 exercises 1989 edition

Abstract: In narrow-band systems electrons can interact with each other via a short-range nonretarded attractive potential. The origin of such an effective local attraction can be polaronic or it can be due to a coupling between electrons and excitons or plasmons. It can also result from purely chemical (electronic) mechanisms, especially in compounds with elements favoring disproportionation of valent states. These mechanisms are discussed and an exhaustive list of materials in which such local electron pairing occurs is given. The authors review the thermodynamic and electromagnetic properties of such systems in several limiting scenarios: (i) Systems with on-site pairing which can be described by the extended negative-$U$ Hubbard model. The strong-attraction limit of this model, at which it reduces to a system of tightly bound electron pairs (bipolarons) on a lattice, is extensively discussed. These electron pairs behaving as hard-core charged bosons can exhibit a superconducting state analogous to that of superfluid $^{4}\mathrm{He}$ II. The change-over from weak-attraction BCS-like superconductivity to the superfluidity of charged hard-core bosons is examined. (ii) Systems with intersite pairing described by an extended Hubbard model with $Ug0$ and nearest-neighbor attraction and/or nearest-neighbor spin exchange as well as correlated hopping. (iii) A mixture of local pairs and itinerant electrons interacting via a charge-exchange mechanism giving rise to a mutually induced superconductivity in both subsystems. The authors discuss to what extent the picture of local pairing, and in particular superfluidity of hard-core charged bosons on a lattice, can be an explanation for the superconducting and normal-state properties of the high-${T}_{c}$ oxides: doped BaBi${\mathrm{O}}_{3}$ and the cuprates.

Abstract: In previous publications, it was shown that an efficient local coupled cluster method with single- and double excitations can be based on the concept of pair natural orbitals (PNOs) [F. Neese, A. Hansen, and D. G. Liakos, J. Chem. Phys. 131, 064103 (2009)]. The resulting local pair natural orbital-coupled-cluster single double (LPNO-CCSD) method has since been proven to be highly reliable and efficient. For large molecules, the number of amplitudes to be determined is reduced by a factor of 10(5)-10(6) relative to a canonical CCSD calculation on the same system with the same basis set. In the original method, the PNOs were expanded in the set of canonical virtual orbitals and single excitations were not truncated. This led to a number of fifth order scaling steps that eventually rendered the method computationally expensive for large molecules (e.g., >100 atoms). In the present work, these limitations are overcome by a complete redesign of the LPNO-CCSD method. The new method is based on the combination of the concepts of PNOs and projected atomic orbitals (PAOs). Thus, each PNO is expanded in a set of PAOs that in turn belong to a given electron pair specific domain. In this way, it is possible to fully exploit locality while maintaining the extremely high compactness of the original LPNO-CCSD wavefunction. No terms are dropped from the CCSD equations and domains are chosen conservatively. The correlation energy loss due to the domains remains below 8800 basis functions and >450 atoms. In all larger test calculations done so far, the LPNO-CCSD step took less time than the preceding Hartree-Fock calculation, provided no approximations have been introduced in the latter. Thus, based on the present development reliable CCSD calculations on large molecules with unprecedented efficiency and accuracy are realized.