Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems

Huntington, Lee M. J.; Hansen, Andreas; Neese, Frank; Nooijen, Marcel

doi:doi:10.1063/1.3682325

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Communication: Thermodynamics of condensed matter with strong pressure-energy correlations

We show that for any liquid or solid with strong correlation between its NVT virial and potential-energy equilibrium fluctuations, the temperature is a product of a function of excess entropy per particle and a function of density, T = f(s)h(ρ). This implies that (1) the system's isomorphs (curves in the phase diagram of invariant structure and dynamics) are described by h(ρ)/T = Const., (2) the density-scaling exponent is a function of density only, and (3) a Grüneisen-type equation of state ap...

Revised self-consistent continuum solvation in electronic-structure calculations

The solvation model proposed by Fattebert and Gygi [J. Comput. Chem. 23, 662 (2002)10.1002/jcc.10069] and Scherlis et al. [J. Chem. Phys. 124, 074103 (2006)10.1063/1.2168456] is reformulated, overcoming some of the numerical limitations encountered and extending its range of applicability. We first recast the problem in terms of induced polarization charges that act as a direct mapping of the self-consistent continuum dielectric; this allows to define a functional form for the dielectric that is...

We have recently introduced a parameterized coupled-cluster singles and doubles model (pCCSD(α, β)) that consists of a bivariate parameterization of the CCSD equations and is inspired by the coupled electron pair approximations. In our previous work, it was demonstrated that the pCCSD(−1, 1) method is an improvement over CCSD for the calculation of geometries, harmonic frequencies, and potential energy surfaces for single bond-breaking. In this paper, we find suitable pCCSD parameters for applications in reaction thermochemistry and thermochemical kinetics. The motivation is to develop an accurate and economical methodology that, when coupled with a robust local correlation framework based on localized pair natural orbitals, is suitable for large-scale thermochemical applications for sizeable molecular systems. It is demonstrated that the original pCCSD(−1, 1) method and several other pCCSD methods are a significant improvement upon the standard CCSD approach and that these methods often approach the accuracy of CCSD(T) for the calculation of reaction energies and barrier heights. We also show that a local version of the pCCSD methodology, implemented within the local pair natural orbital (LPNO) based CCSD code in ORCA, is sufficiently accurate for wide-scale chemical applications. The LPNO based methodology allows us for routine applications to intermediate sized (20–100 atoms) molecular systems and is a significantly more accurate alternative to MP2 and density functional theory for the prediction of reaction energies and barrier heights.

Article Outline

INTRODUCTION
THEORY
BENCHMARK CALCULATIONS
1. Computational details
2. Optimization of pCCSD parameters
3. Benchmark calculations on reaction energies of the fit set
4. Molecular electronic energies, atomization energies and hydrogenation energies for the molecules from the fit set
5. Barrier heights for small molecules
6. Performance of LPNO-pCCSD methods for the calculation of reaction energies and barrier heights
7. Transition metal carbonyl dissociation energies
CONCLUDING REMARKS

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KEYWORDS and PACS

Keywords

bonds (chemical), coupled cluster calculations, molecular configurations, orbital calculations, potential energy surfaces, reaction kinetics theory, thermochemistry

PACS

31.15.bw

Coupled-cluster theory
31.50.-x

Potential energy surfaces
33.15.Bh

General molecular conformation and symmetry; stereochemistry
33.15.Fm

Bond strengths, dissociation energies
82.20.Kh

Potential energy surfaces for chemical reactions
82.60.-s

Chemical thermodynamics

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3682325

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

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