Search results for "Møller–Plesset perturbation theory"
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NMR chemical shift computations at second-order Møller-Plesset perturbation theory using gauge-including atomic orbitals and Cholesky-decomposed two-…
2021
We report on a formulation and implementation of a scheme to compute NMR shieldings at second-order Moller-Plesset (MP2) perturbation theory using gauge-including atomic orbitals (GIAOs) to ensure gauge-origin independence and Cholesky decomposition (CD) to handle unperturbed as well as perturbed two-electron integrals. We investigate the accuracy of the CD for the derivatives of the two-electron integrals with respect to an external magnetic field as well as for the computed NMR shieldings, before we illustrate the applicability of our CD based GIAO-MP2 scheme in calculations involving up to about one hundred atoms and more than one thousand basis functions.
Time-Independent Canonical Perturbation Theory
2001
First we consider the perturbation calculation only to first order, limiting ourselves to only one degree of freedom. Furthermore, the system is to be conservative, ∂ H∕∂ t = 0, and periodic in both the unperturbed and perturbed case. In addition to periodicity, we shall require the Hamilton–Jacobi equation to be separable for the unperturbed situation. The unperturbed problem H0(J0) which is described by the action-angle variables J0 and w0 will be assumed to be solved. Thus we have, for the unperturbed frequency: $$\displaystyle{ \nu _{0} = \frac{\partial H_{0}} {\partial J_{0}} }$$ (10.1) and $$\displaystyle{ w_{0} =\nu _{0}t +\beta _{0}\;. }$$ (10.2) Then the new Hamiltonian reads, up t…