Rigorously extensive orbital-invariant renormalized perturbative triples corrections from quasi-variational coupled cluster theory.

نویسندگان

  • James B Robinson
  • Peter J Knowles
چکیده

We show that, by making use of the linked tensor objects inherent to the approach, Orbital-optimised Quasi-Variational Coupled Cluster Theory (OQVCCD) leads naturally to a computationally-trivial, rigorously extensive, and orbital-invariant renormalization of the standard (T) correction for the perturbative inclusion of the effects of connected triple excitations. The resulting prototype method, renormalized perturbative triple OQVCCD (R-OQVCCD(T)), is demonstrated to predict potential energy curves for single bond-breaking processes of significantly higher accuracy than OQVCCD with the standard perturbative triple-excitation correction (OQVCCD(T)) itself, and to be in good numerical correspondence with the existing renormalized (R-CCSD(T)) and completely renormalized (CR-CCSD(T)) coupled-cluster singles doubles triples methods, while continuing to provide descriptions of multiple bond-breaking processes of OQVCCD(T) quality.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Approximate variational coupled cluster theory.

We show that it is possible to construct an accurate approximation to the variational coupled cluster method, limited to double substitutions, from the minimization of a functional that is rigorously extensive, exact for isolated two-electron subsystems and invariant to transformations of the underlying orbital basis. This approximate variational coupled cluster theory is a modification and enh...

متن کامل

Variational formulation of perturbative explicitly-correlated coupled-cluster methods.

We present a variational formulation of the recently-proposed CCSD(2)(R12) method [Valeev, Phys. Chem. Chem. Phys., 2008, 10, 106]. The centerpiece of this approach is the CCSD(2)(R12) Lagrangian obtained via Löwdin partitioning of the coupled-cluster singles and doubles (CCSD) Hamiltonian. Extremization of the Lagrangian yields the second-order basis set incompleteness correction for the CCSD ...

متن کامل

Scaling reduction of the perturbative triples correction „T... to coupled cluster theory via Laplace transform formalism

A reformulation of the perturbative triples correction to coupled cluster singles and doubles ~CCSD! based on the numerical Laplace transform of the energy denominator is presented. Rearranged equations reduce the O(N7) canonical scaling to O(N6), where N is a size measure of the electronic system. Two to three quadrature points is adequate for chemical predictions. The Laplace ansatz permits s...

متن کامل

Breaking multiple covalent bonds with Hartree-Fock-based quantum chemistry: Quasi-Variational Coupled Cluster theory with perturbative treatment of triple excitations.

We enhance the recently proposed Optimized-orbital Quasi-Variational Coupled Cluster Doubles (OQVCCD) method for the calculation of ground-state molecular electronic structure by augmenting it with the standard perturbative (T) correction for the effects of connected triple excitations. We demonstrate the OQVCCD(T) ansatz to be outstandingly robust and accurate in the description of the breakin...

متن کامل

The orbital-specific virtual local triples correction: OSV-L(T).

A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schütz [J. Chem. Phys. 113, 9986 (2000)], the new scheme works without any ad hoc truncations of the virtual space to domains. A single thresho...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • The Journal of chemical physics

دوره 138 7  شماره 

صفحات  -

تاریخ انتشار 2013