The vibrational spectra of furoxan and dichlorofuroxan: A comparative theoretical study using density functional theory and local electron correlation methods

Rauhut, Guntram; Werner, Hans‐Joachim

doi:10.1039/b212590k

Cited by 34 publications

(23 citation statements)

References 46 publications

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“…I-III is available in the MOLPRO package of ab initio programs 85,86 and has already been successfully applied in various applications. 19,76,77,[87][88][89][90] For example, barrier heights in various enzymes have been computed in the framework of the hybrid quantum mechanical and molecular mechanics (QM/MM) approach, and the effect of domain and pair approximations on the results has been systematically investigated. 76,77,90 Furthermore, the accuracy of the local coupled cluster method (without density fitting) has been tested for reaction energies 17 and other molecular properties, such as dipole moments and dipole polarizabilities.…”

Section: Sample Calculationsmentioning

confidence: 99%

“…Similar BSSE effects have, for example, also been found in calculations of vibrational frequencies, where the local results were found to be more accurate than the canonical ones. 87,88 In order to account for all effects appropriately, we recommend to add a correction �E MP2(CBS) = E MP2(CBS) − E LMP2 to the LCCSD(T0) results. Alternatively, in Ref.…”

Section: Sample Calculationsmentioning

confidence: 99%

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An efficient local coupled cluster method for accurate thermochemistry of large systems

Werner

Schütz

2011

The Journal of Chemical Physics

Self Cite

268

302

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An efficient local coupled cluster method with single and double excitation operators and perturbative treatment of triple excitations [DF-LCCSD(T)] is described. All required two-electron integrals are evaluated using density fitting approximations. These have a negligible effect on the accuracy but reduce the computational effort by 1-2 orders of magnitude, as compared to standard integral-direct methods. Excitations are restricted to local subsets of non-orthogonal virtual orbitals (domain approximation). Depending on distance criteria, the correlated electron pairs are classified into strong, close, weak, and very distant pairs. Only strong pairs, which typically account for more than 90% of the correlation energy, are optimized in the LCCSD treatment. The remaining close and weak pairs are approximated by LMP2 (local second-order Møller-Plesset perturbation theory); very distant pairs are neglected. It is demonstrated that the accuracy of this scheme can be significantly improved by including the close pair LMP2 amplitudes in the LCCSD equations, as well as in the perturbative treatment of the triples excitations. Using this ansatz for the wavefunction, the evaluation and transformation of the two-electron integrals scale cubically with molecular size. If local density fitting approximations are activated, this is reduced to linear scaling. The LCCSD iterations scale quadratically, but linear scaling can be achieved by neglecting some terms involving contractions of single excitations. The accuracy and efficiency of the method is systematically tested using various approximations, and calculations for molecules with up to 90 atoms and 2636 basis functions are presented.

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Section: Sample Calculationsmentioning

confidence: 99%

Section: Sample Calculationsmentioning

confidence: 99%

An efficient local coupled cluster method for accurate thermochemistry of large systems

Werner

Schütz

2011

The Journal of Chemical Physics

Self Cite

268

302

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“…For matrix products of twoelectron integrals with other tensors, Friesner and Carter invoked the pseudospectral approach for calculating twoelectron integrals and gained even more computational savings than before. Subsequently, over the past decade, Schütz and Werner [4,[20][21][22][23][24][25][26][27][28][29][30][31] have applied and updated these methods to a wide variety of locally correlated electronic structure methods, including LCCSD, achieving a linear scaling algorithm in certain regimes. According to their approach, one divides up the amplitudes into strong, moderate, weak and very weak amplitudes and treats the different amplitudes at different theoretical levels.…”

Section: Historical Overviewmentioning

confidence: 99%

Self-Tailored One-Dimensional ZnO Nanodot Arrays Formed by Metalorganic Chemical Vapor Deposition

Kim

Ueda

Kotani

et al. 2003

Jpn. J. Appl. Phys.

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Local coupled-cluster singles-doubles theory (LCCSD) is a theorist's attempt to capture electron-electron correlation in a fast amount of time and with chemical accuracy. Many of the difficult computational hurdles have been navigated over the last twenty years, including how to construct a linear scaling algorithm and how to produce smooth potential energy surfaces. Nevertheless, there remains the question of just how accurate a local correlation model can be, and what are the chemical limits within which local models are largely applicable. Here, we investigate how accurately can LCCSD approximate full CCSD for cases of atomization energies, isomerization energies, conformational energies, barrier heights and electron affinities. Our conclusion is that LCCSD computes relative energies that are correct to within 1-2 kcal mol −1 of the CCSD energy using relatively aggressive cutoffs and over a broad range of different molecular environments-alkane isomers, dipeptide conformations, Diels-Alder transition states and electron attachment in charge delocalized systems. These findings should push the reach of local correlation applications into new research terrain, including molecules on metal cluster surfaces or perhaps even metal-molecule-metal clusters.

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“…In order to make correlation energies computationally tractable, many local correlation schemes have been introduced over the last 20 years ͑mostly at the perturbative or MP2 level͒ beginning with Saebo and Pulay, [8][9][10][11][12] and later developed by Carter, 13 Friesner, 14 Schütz and Werner,[15][16][17][18][19][20][21][22][23][24][25][26][27] and many others. The basic premise behind local correlation calculations is to localize all canonical molecular orbitals, and then correlate only those localized molecular orbitals which are close to each other in physical, three-dimensional space ͑R 3 ͒.…”

Section: Introductionmentioning

confidence: 99%

A near linear-scaling smooth local coupled cluster algorithm for electronic structure

Subotnik

Sodt

Head‐Gordon

2006

The Journal of Chemical Physics

134

108

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Articles you may be interested inRelativistic coupled-cluster calculations on XeF6: Delicate interplay between electron-correlation and basis-set effects Divide-and-conquer-based linear-scaling approach for traditional and renormalized coupled cluster methods with single, double, and noniterative triple excitations Transferability in the natural linear-scaled coupled-cluster effective Hamiltonian approach: Applications to dynamic polarizabilities and dispersion coefficients A natural linear scaling coupled-cluster methodWe demonstrate near linear scaling of a new algorithm for computing smooth local coupled-cluster singles-doubles ͑LCCSD͒ correlation energies of quantum mechanical systems. The theory behind our approach has been described previously, ͓J. Subotnik and M. Head-Gordon, J. Chem. Phys. 123, 064108 ͑2005͔͒, and requires appropriately multiplying standard iterative amplitude equations by a bump function, creating local amplitude equations ͑which are smooth according to the implicit function theorem͒. Here, we provide an example that this theory works in practice: we show that our algorithm leads to smooth potential energy surfaces and yields large computational savings. As an example, we apply our LCCSD approach to measure the post-MP2 correction to the energetic gap between two different alanine tetrapeptide conformations.

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The vibrational spectra of furoxan and dichlorofuroxan: A comparative theoretical study using density functional theory and local electron correlation methods

Cited by 34 publications

References 46 publications

An efficient local coupled cluster method for accurate thermochemistry of large systems

An efficient local coupled cluster method for accurate thermochemistry of large systems

Self-Tailored One-Dimensional ZnO Nanodot Arrays Formed by Metalorganic Chemical Vapor Deposition

A near linear-scaling smooth local coupled cluster algorithm for electronic structure

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