Journal ArticleDOI
Orbital-invariant formulation and second-order gradient evaluation in MOller-Plesset perturbation theory
Peter Pulay,Svein Saebo +1 more
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In this article, the second and third orders of Moller-Plesset perturbation theory are reformulated in terms of arbitrary (e.g., localized) internal orbitals, and atomic orbitals in the virtual space.Abstract:
Based on the Hylleraas functional form, the second and third orders of Moller-Plesset perturbation theory are reformulated in terms of arbitrary (e.g., localized) internal orbitals, and atomic orbitals in the virtual space. The results are strictly equivalent to the canonical formulation if no further approximations are introduced. The new formalism permits the extension of the local correlation method to Moller-Plesset theory. It also facilitates the treatment of weak pairs at a lower (e.g., second order) level of theory in CI and coupled cluster methods. Based on our formalism, an MP2 gradient algorithm is outlined which does not require the storage of derivative integrals, integrals with three external MO indices, and, using the method of Handy and Schaefer, the repeated solution of the coupled-perturbed SCF equations.read more
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A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms
TL;DR: In this paper, an open-shell complete basis set (CBS) model chemistry, based on the unrestricted Hartree-Fock (UHF) zero-order wave function, is defined to include corrections for basis set truncation errors.
Journal ArticleDOI
CC2 excitation energy calculations on large molecules using the resolution of the identity approximation
Christof Hättig,Florian Weigend +1 more
TL;DR: A new implementation of the approximate coupled cluster singles and doubles method CC2 is reported, which is suitable for large scale integral-direct calculations and employs the resolution of the identity (RI) approximation for two-electron integrals to reduce the CPU time needed for calculation and I/O of these integrals.
Journal ArticleDOI
Jaguar: A high-performance quantum chemistry software program with strengths in life and materials sciences
Art D. Bochevarov,Edward Harder,Thomas F. Hughes,Jeremy R. Greenwood,Dale A. Braden,Dean M. Philipp,David Rinaldo,Mathew D. Halls,Jing Zhang,Richard A. Friesner +9 more
TL;DR: Jaguar as mentioned in this paper is an ab initio quantum chemical program that specializes in fast electronic structure predictions for molecular systems of medium and large size, such as density functional theory (DFT) and local second-order Moller-Plesset perturbation theory.
Journal ArticleDOI
Local treatment of electron correlation in coupled cluster theory
TL;DR: In this paper, the closed-shell coupled cluster theory restricted to single and double excitation operators (CCSD) is formulated in a basis of nonorthogonal local correlation functions.
Journal ArticleDOI
Avoiding the integral storage bottleneck in LCAO calculations of electron correlation
Svein Saebo,Jan Almlöf +1 more
TL;DR: In this article, a method for obtaining electron-repulsion integrals over a molecular-orbital basis without any explicit four-index transformation involving input/output is proposed, which allows for calculations that would otherwise be prohibited by storage limitations with conventional techniques.
References
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Journal ArticleDOI
The influence of polarization functions on molecular orbital hydrogenation energies
P. C. Hariharan,John A. Pople +1 more
TL;DR: In this paper, a split-valence extended gaussian basis set was used to obtain the LCAO-MO-SCF energies of closed shell species with two non-hydrogen atoms.
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On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell-Type Expansion Using Quantum-Field Theoretical Methods
TL;DR: In this article, a method for the calculation of the matrix elements of the logarithm of an operator which gives the exact wavefunction when operating on the wavefunction in the one-electron approximation is proposed.
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Ab initio calculation of force constants and equilibrium geometries in polyatomic molecules
TL;DR: In this article, it is suggested that force constants should be calculated by differentiating the forces numerically, which is numerically more accurate and requires less computation than the customary one of differentiating energy numerically twice.
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Theoretical models incorporating electron correlation
TL;DR: In this paper, the perturbation approach originally introduced by Moller and Plesset, terminated at finite order, is compared from the point of view of requirements for theoretical chemical models.