Optimized auxiliary basis sets for explicitly correlated methods

Yousaf, Kazim E.; Peterson, Kirk A.

doi:10.1063/1.3009271

Cited by 495 publications

(381 citation statements)

References 44 publications

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“…108 The Hartree-Fock contribution was corrected with the complementary auxiliary basis set (CABS) singles approach of Knizia and Werner. 109,110 In the explicitly correlated calculations, we used a Slater type correlation factor as proposed by Ten-no.…”

Section: Quantum Chemical Methods and Qce Protocolmentioning

confidence: 99%

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Domaros

Jähnigen

Friedrich

et al. 2016

The Journal of Chemical Physics

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The established quantum cluster equilibrium (QCE) approach is refined and applied to Nmethylformamide (NMF) and its aqueous solution. The QCE method is split into two iterative cycles: one which converges to the liquid phase solution of the QCE equations and another which yields the gas phase. By comparing Gibbs energies, the thermodynamically stable phase at a given temperature and pressure is then chosen. The new methodology avoids metastable solutions and allows a different treatment of the mean-field interactions within the gas and liquid phases. These changes are of crucial importance for the treatment of binary mixtures. For the first time in a QCE study, the cis-trans-isomerism of a species (NMF) is explicitly considered. Cluster geometries and frequencies are calculated using density functional theory (DFT) and complementary coupled cluster single point energies are used to benchmark the DFT results. Independent of the selected quantum-chemical method, a large set of clusters is required for an accurate thermodynamic description of the binary mixture. The liquid phase of neat NMF is found to be dominated by the cyclic trans-NMF pentamer, which can be interpreted as a linear trimer that is stabilized by explicit solvation of two further NMF molecules. This cluster reflects the known hydrogen bond network preferences of neat NMF. C 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license

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Section: Quantum Chemical Methods and Qce Protocolmentioning

confidence: 99%

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Domaros

Jähnigen

Friedrich

et al. 2016

The Journal of Chemical Physics

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“…[214] The resulting OptRI ABSs are compact and produce negligible RI errors compared to the basis set incompleteness error of the underlying OBS, both for correlation and relative energies. Although originally published to match the cc-pVnZ-F12 bases, the same methodology has been used to produce OptRI sets specifically matched to aug-cc-pVnZ bases, [215] to cc-pCVnZ-F12 bases, [51] for the light alkali and alkaline earth elements, [95] and for the group 11 and 12 transition metal elements.…”

Section: Auxiliary Basis Setsmentioning

confidence: 99%

Gaussian basis sets for molecular applications

Hill¹

2012

Int J of Quantum Chemistry

188

155

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The choice of basis set in quantum chemical calculations can have a huge impact on the quality of the results, especially for correlated ab initio methods. This article provides an overview of the development of Gaussian basis sets for molecular calculations, with a focus on four popular families of modern atom-centered, energy-optimized bases: atomic natural orbital, correlation consistent, polarization consistent, and def2. The terminology used for describing basis sets is briefly covered, along with an overview of the auxiliary basis sets used in a number of integral approximation techniques and an outlook on possible future directions of basis set design.

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“…RSPT2, MRCI and CCSD(T)}. 25 The basis sets 26,27,28,29,30,31,32 employed in the present study for various frozen core (FC) F12…”

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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Optimized auxiliary basis sets for explicitly correlated methods

Cited by 495 publications

References 44 publications

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

Gaussian basis sets for molecular applications

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

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