𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Intermolecular perturbation theory: Renormalized interaction energies

✍ Scribed by William H. Adams


Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
993 KB
Volume
60
Category
Article
ISSN
0020-7608

No coin nor oath required. For personal study only.

✦ Synopsis


For intermolecular perturbation theories in which it is assumed that the unperturbed wave function of the composite system is a product of the unperturbed wave functions of its components, and which satisfy one general constraint, we derive two renormalized interaction energy expressions which are more accurate than the perturbation expansions, when all are evaluated to comparable order. This is accomplished by focusing on the parameter A in terms of which the perturbation expansions are derived rather than on the potential of interaction between components. In the derivation of each renormalized energy formula, we discard zeroth-through infinite-order terms which do not contribute to the interaction energy when the interaction is turned on fully, i.e., when A = 1. The first renormalized interaction energy when A = 1 is identical in form to the interaction energy in the symmetrized Rayleigh-Schrodinger (SRS) theory, but not in interpretation. The wave function appearing in the renormalized energy cannot generally be that assumed in the SRS theory, and the renormalized energy to zeroth order in A is not zero. The latter is not surprising because we discarded a zeroth-order term in the derivation. The second renormalized interaction energy formula is derived from the first by using the same set of assumptions and arguments that were used in deriving the first. We expect it to be more accurate than the first, which is expected to be more accurate than the sum of the perturbation energies, all evaluated to comparable order. These expectations are supported by the results of calculations on LiH using two perturbation theories, the polarization approximation and the Amos-Musher theory. The first-order wave functions for both were calculated in the configuration interaction (CI) approximation; then the interaction energies were calculated by summing the perturbation energies through third order and by evaluating the renormalized energy expressions. The perturbation results are compared to interaction energies calculated by full CI with the same basis set. As important as the formulas is the light our analysis throws on the meaning of order in intermolecular perturbation theory.


πŸ“œ SIMILAR VOLUMES


Quantum Field Theory || Perturbative Ren
✍ Huang, Kerson πŸ“‚ Article πŸ“… 1998 πŸ› Wiley-VCH Verlag GmbH 🌐 English βš– 883 KB

Quantum field theory is frequently approached from the perspective of particle physics. This book adopts a more general point of view and includes applications of condensed matter physics. Written by a highly respected writer and researcher, it first develops traditional concepts, including Feynman

Renormalized Perturbation Theory for Qua
✍ J. Zamastil; J. Čı́žek; L. SkΓ‘la πŸ“‚ Article πŸ“… 1999 πŸ› Elsevier Science 🌐 English βš– 224 KB

The analytic structure of the renormalized energy of the quartic anharmonic oscillator described by the Hamiltonian H= p 2 +x 2 +;x 4 is discussed and the dispersion relation for the renormalized energy is found. It follows from the analytic structure that the renormalized strong coupling expansion

Comparison of basis set superposition er
✍ G. J. HalΓ‘sz; Á. VibΓ³k; I. Mayer πŸ“‚ Article πŸ“… 1999 πŸ› John Wiley and Sons 🌐 English βš– 281 KB πŸ‘ 2 views

Recently, two different but conceptually similar basis set Ε½ . superposition error BSSE free second-order perturbation theoretical schemes were developed by us that are being based on the chemical Hamiltonian Ε½ . approach CHA . Using these CHA-MP2 and CHA-PT2 methods, a comparison is made between th

Renormalization of Chiral Perturbation T
✍ J. Bijnens; G. Colangelo; G. Ecker πŸ“‚ Article πŸ“… 2000 πŸ› Elsevier Science 🌐 English βš– 401 KB

The renormalization of chiral perturbation theory is carried out to next-to-next-to-leading order in the meson sector. We calculate the divergent part of the generating functional of Green functions of quark currents to O( p 6 ) for chiral SU(n), involving one-and two-loop diagrams. The renormalizat