Approaching the Basis Set Limit in Density Functional Theory Calculations Using Dual Basis Sets without Diagonalization

Liang, Weifa; Head‐Gordon, Martin

doi:10.1021/jp0374713

Cited by 86 publications

(106 citation statements)

References 27 publications

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“…The energy lowering due to electron transfer from the occupied ALMOs on molecule x to the virtual orbitals of molecule y in Eq. 12 is a quasi-perturbative energy correction 50,56,57 that can be expressed as:…”

Section: B Decomposition Analysis Based On Absolutely Localized Molementioning

confidence: 99%

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water clusters and bulk water. CONTENTS

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Section: B Decomposition Analysis Based On Absolutely Localized Molementioning

confidence: 99%

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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“…This method mixes SCF and DFT exchange with DFT and MP2 correlation energy then corrects the dispersion energy empirically using Grimme's D3 correction. 24 To facilitate calculations of even larger molecules, we have recently implemented 25 in GAMESS the dual-basis [26][27][28][29][30] SCF method. Here the SCF energy is approximated by a converged small (truncated) basis energy calculation.…”

Section: E(ccsd) − E(mp2) ∆Ccsd(t) = E(ccsd(t)) − E(mp2) and ∆(T) =mentioning

confidence: 99%

At What Chain Length Do Unbranched Alkanes Prefer Folded Conformations?

2014

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Short unbranched alkanes are known to prefer linear conformations, while long unbranched alkanes are folded. It is not known with certainty at what chain length the linear conformation is no longer the global minimum. To clarify this point, we use ab initio and density functional methods to compute the relative energies of the linear and hairpin alkane conformers for increasing chain lengths. Extensive electronic structure calculations are performed to obtain optimized geometries, harmonic frequencies and accurate single point energies for the selected alkane conformers from octane through octadecane. Benchmark CCSD(T)/cc-pVTZ single point calculations are performed for chains through tetradecane, while approximate methods are required for the longer chains up to octadecane. Using frozen natural orbitals to unambiguously truncate the virtual orbital space, we are able to compute composite CCSD FNO(T) single point energies for all the chain lengths. This approximate composite method has significant computational savings compared to full CCSD(T) while retaining ∼ 0.15 kcal/mol accuracy compared to the benchmark results. More approximate dual-basis resolutionof-the-identity double-hybrid DFT calculations are also performed and shown to have reasonable 0.2 − 0.4 kcal/mol errors compared with our benchmark values. After including contributions from temperature dependent internal energy shifts, we find the preference for folded conformations to lie between hexadecane and octadecane, in excellent agreement with recent experiments [Lüttschwager, N. O.; Wassermann, T. N.; Mata, R. A.; Suhm, M. A.

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“…Our method is motivated by the dual-level DFT method of Nakajima and Hirao 9 and the dual grid scheme of Tozer et al 10 We combine these with dual basis ideas [11][12][13][14][15][16][17][18][19] to obtain a triple perturbation in the functional, basis and grid dimensions.…”

Section: Introductionmentioning

confidence: 99%

Density functional triple jumping

Deng

Gilbert

Gill

2010

Phys. Chem. Chem. Phys.

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We propose a density functional perturbative scheme to approximate the energy of a high-level DFT calculation at a significantly reduced cost. Our approach involves performing a primary SCF calculation using a crude functional, basis set and quadrature grid, followed by a single step using a more sophisticated secondary functional, basis and grid. Unlike the earlier dual-level DFT approach of Nakajima and Hirao, we use Roothaan diagonalization instead of perturbation theory to incorporate the effects of the secondary basis set. We show that energies at the popular B3LYP/6-311+G(3df,2p)/(75,302) level can be accurately estimated from primary calculations at the relatively economical BLYP/6-31G(d)/SG-0 level.

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Approaching the Basis Set Limit in Density Functional Theory Calculations Using Dual Basis Sets without Diagonalization

Cited by 86 publications

References 27 publications

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

At What Chain Length Do Unbranched Alkanes Prefer Folded Conformations?

Density functional triple jumping

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