Frontiers in electronic structure theory

Sherrill, C. David

doi:10.1063/1.3369628

Cited by 170 publications

(165 citation statements)

References 182 publications

(176 reference statements)

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“…333 Applicability of CCSD(T) is, however, hampered by the size of the modeled system and is limited to the cluster approach. Indeed, the main disadvantage of wave function based correlated methods is the high scaling of the computational cost with the size of the system.…”

Section: Wave Function Based Methodsmentioning

confidence: 99%

“…With all dangling bonds properly healed, the cluster becomes a regular molecule so that standard quantum mechanical methods using highly sophisticated quantum chemistry computer programs can be applied to characterize its physico-chemical features. This is a real advantage over the PBC method, as the level of sophistication in the adopted theoretical method is only limited by the available computing resources, so that CCSD(T), the golden standard for quantum chemical calculations, 333 can be adopted. Furthermore, solvation methods based on the continuum approach 334 can also be included as a first approximation to study solvent effects on the adsorptive properties of the surface "active site", which is particularly important in the context of biomolecules adsorption.…”

Section: The Cluster Approachmentioning

confidence: 99%

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Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

et al. 2013

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Section: Wave Function Based Methodsmentioning

confidence: 99%

Section: The Cluster Approachmentioning

confidence: 99%

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

et al. 2013

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“…Since explicitly correlated methods are known to accelerate convergence of computed correlation energies toward the complete basis set limit, 24 using a small basis set (e.g. TZ quality) with these F12 methods is expected to produce results comparable to using a large basis set (e.g.…”

Section: Geometry Optimization Calculationsmentioning

confidence: 99%

Simulation of the single-vibronic-level emission spectra of HAsO and DAsO

Mok

Lee

Dyke

2016

The Journal of Chemical Physics

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The single-vibronic-level emission spectra of HAsO and DAsO have been simulated by electronic structure/Franck-Condon factor calculations to confirm the spectral molecular carrier and to investigate the electronic states involved. Various multi-reference (MR) methods, namely NEVPT2 (n-electron valence state second order perturbation theory), RSPT2-F12 (explicitly correlated Rayleigh-Schrodinger second order perturbation theory) and MRCI-F12 (explicitly correlated multi-reference configuration interaction), were employed to compute the geometries and relative electronic energies for the X 1 A' and Ã 1 A" states of HAsO. These are the highest level calculations on these states yet reported. The MRCI-F12 method gives computed T 0 (adiabatic transition energy including zero-point energy correction) values which agree well with the available experimental T 0 value, much better than previously computed values and values computed with other MR methods in this work. In addition, the potential energy surfaces of the X 1 A' and Ã 1 A" states of HAsO were computed using the MRCI-F12 method. Franck-Condon factors between the two states, which include anharmonicity and Duschinsky rotation, were then computed and used to simulate the recently reported single-vibronic-level (SVL) emission spectra of HAsO and DAsO [Grimminger and Clouthier, J. Chem. Phys. 135, 184308 (2011)]. Our simulated SVL emission spectra confirm the assignments of the molecular carrier, electronic states involved and the vibrational structures observed in the SVL emission spectra, but suggest a loss of intensity in the reported experimental spectra at the low emission energy region, almost certainly due to a loss of responsivity near the cut off region (~800 nm) of the detector used. Computed and experimentally 2 derived r e (equilibrium) and/or r 0 {the (0,0,0) vibrational level} geometries of the two states of HAsO are discussed. a)

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“…29,30 However, despite the promise of local coupled cluster methods, existing approaches have not yet found widespread application. 16 Here, we pursue an alternative strategy that does not rely explicitly on spatial locality. We propose to apply the recently developed least-squares THC representation (LS-THC) 31 to the doubles amplitudes as well as the ERIs in CCSD.…”

Section: Introductionmentioning

confidence: 99%

Communication: Tensor hypercontraction. III. Least-squares tensor hypercontraction for the determination of correlated wavefunctions

Hohenstein

Parrish

Sherrill

et al. 2012

The Journal of Chemical Physics

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173

197

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ARTICLES YOU MAY BE INTERESTED INThe manipulation of the rank-four tensor of double excitation amplitudes represents a challenge to the efficient implementation of many electronic structure methods. We present a proof of concept for the approximation of doubles amplitudes in the tensor hypercontraction (THC) representation. In particular, we show how THC can be used to both reduce the scaling with respect to molecular size of coupled cluster singles and doubles (CCSD) (and related methods) by two orders [from O(N 6 ) to O(N 4 )] and remove the memory bottleneck associated with storage of the doubles amplitudes. The accuracy of correlated methods as integral and amplitude approximations are introduced is examined. For a set of 20 small molecules, single and double-excitation configuration interaction (CISD), quadratic CISD (QCISD), and CCSD correlation energies could be reproduced with millihartree accuracy after the introduction of these approximations. Our approach exploits otherwise hidden factorizable tensor structure in both the electron repulsion integrals and the wavefunction coefficients and should be applicable with suitable modifications to many methods in electronic structure theory.

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Frontiers in electronic structure theory

Abstract: Perspective: Explicitly correlated electronic structure theory for complex systems

Cited by 170 publications

References 182 publications

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

Simulation of the single-vibronic-level emission spectra of HAsO and DAsO

Communication: Tensor hypercontraction. III. Least-squares tensor hypercontraction for the determination of correlated wavefunctions

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