Theoretical interpretation of Grimme’s spin-component-scaled second order Møller-Plesset theory

Szabados, Ágnes

doi:10.1063/1.2404660

Cited by 98 publications

(85 citation statements)

References 45 publications

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“…where p OS and p SS are empirical (but theoretically wellfounded) scaling factors with values of 6/5 and 1/3, respectively, which have been obtained from a fit to a set of representative reaction energies 9 (for a recent theoretical derivation of the scaling factors see ref 10). This SCS-MP2 approach differs from standard MP2, where both components contribute equally (i.e., p OS ) p SS ) 1).…”

Section: Theory Of Our Approachesmentioning

confidence: 99%

Theoretical Thermodynamics for Large Molecules: Walking the Thin Line between Accuracy and Computational Cost

2008

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The thermodynamic properties of molecules are of fundamental interest in physics, chemistry, and biology. This Account deals with the developments that we have made in the about last five years to find quantum chemical electronic structure methods that have the prospect of being applicable to larger molecules. The typical target accuracy is about 0.5-1 kcal mol(-1) for chemical reaction and 0.1 kcal mol(-1) for conformational energies. These goals can be achieved when a few physically motivated corrections to first-principles methods are introduced to standard quantum chemical techniques. These do not lead to a significantly increased computational expense, and thus our methods have the computer hardware requirements of the corresponding standard treatments. Together with the use of density-fitting (RI) integral approximations, routine computations on systems with about 100 non-hydrogen atoms (2000-4000 basis functions) can be performed on modern PCs. Our improvements regarding accuracy are basically due to the use of modified second-order perturbation theory to account for many-particle (electron correlation) effects. Such nonlocal correlations are responsible for important parts of the interaction in and between atoms and molecules. A common example is the long-range dispersion interaction that lead to van der Waals complexes, but as shown here also the conventional thermodynamics of large molecules is significantly influenced by intramolecular dispersion effects. We first present the basic theoretical ideas behind our approaches, which are the spin-component-scaled Møller-Plesset perturbation theory (SCS-MP2) and double-hybrid density functionals (DHDF). Furthermore, the effect of the independently developed empirical dispersion correction (DFT-D) is discussed. Together with the use of large atomic orbital basis sets (of at least triple- or quadruple-zeta quality), the accuracy of the new methods is even competitive with computationally very expensive coupled-cluster methods, but they still remain routinely applicable for day-to-day chemical problems. This is demonstrated for the G3/99 benchmark set of heats of formation, 34 organic isomerization energies, and barriers for a number of pericyclic reactions. As an electronically complicated example, the relative energies of three isomeric Au(8) clusters are considered. In general, we recommend the very robust B2PLYP-D density functional approach for heat of formation calculations and for electronically complicated situations like transition metal complexes or open-shell species. With B2PLYP-D, an unprecedented low mean absolute deviation for the G3/99 test set with a DFT approach of 1.7 kcal mol(-1) has been achieved. For closed-shell main-group molecules and many relative energies, SCS-MP2 is the method of choice, because it completely avoids the self-interaction error problem that still plagues current DFT. In critical cases, it is recommended to apply SCS-MP2 and B2PLYP-D simultaneously, where also the comparison with standard MP2 and density functionals like...

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Section: Theory Of Our Approachesmentioning

confidence: 99%

Theoretical Thermodynamics for Large Molecules: Walking the Thin Line between Accuracy and Computational Cost

2008

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“…A theoretically well-known procedure to combine information from the second and third-orders of perturbation theory is Feenberg scaling, which has recently been discussed in the context of the SCS idea. [28] However, this approach lacks size-consistency and is therefore not suited for the computation of interaction energies.…”

Section: Eðccsdðtþ=small Basisþàeðmp2=small Basisþ: ð4þmentioning

confidence: 99%

Scaled MP3 Non‐Covalent Interaction Energies Agree Closely with Accurate CCSD(T) Benchmark Data

et al. 2009

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Scaled MP3 interaction energies calculated as a sum of MP2/CBS (complete basis set limit) interaction energies and scaled third-order energy contributions obtained in small or medium size basis sets agree very closely with the estimated CCSD(T)/CBS interaction energies for the 22 H-bonded, dispersion-controlled and mixed non-covalent complexes from the S22 data set. Performance of this so-called MP2.5 (third-order scaling factor of 0.5) method has also been tested for 33 nucleic acid base pairs and two stacked conformers of porphine dimer. In all the test cases, performance of the MP2.5 method was shown to be superior to the scaled spin-component MP2 based methods, e.g. SCS-MP2, SCSN-MP2 and SCS(MI)-MP2. In particular, a very balanced treatment of hydrogen-bonded compared to stacked complexes is achieved with MP2.5. The main advantage of the approach is that it employs only a single empirical parameter and is thus biased by two rigorously defined, asymptotically correct ab-initio methods, MP2 and MP3. The method is proposed as an accurate but computationally feasible alternative to CCSD(T) for the computation of the properties of various kinds of non-covalently bound systems.

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“…The SCS-MP2 variant makes use of the original SCS scheme (c os = 1.20 and c ss = 0.33) proposed by Grimme [27] but many modifications of the original scheme were also proposed [28,[30][31][32][33][34]. Aside from SCS-MP2, other four variants that can be expressed by the respective SCS schemes, namely SOS-MP2 [28], FE2-MP2 [30], SCS(MI)-MP2 [31], and S2-MP [34], were adopted in the present work. These four variants differ in the values of the c os and c ss coefficients from the original SCS scheme.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Theoretical investigation of the N → Sn coordination in (Me3SnCN)2

Matczak

2014

Struct Chem

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The N → Sn coordination occurring in the (Me 3 SnCN) 2 dimer has been investigated using various computational methods and several theoretical tools possessing great interpretative potential. The dimer is formed by moving the C≡N fragment of the first Me 3 SnCN molecule close to the Sn atom of the second molecule and the resulting N → Sn coordination corresponds to that observed in the crystal structure of trimethyltin cyanide. The geometry of (Me 3 SnCN) 2 is optimized using the MP2 method and its 11 variants, and then it is compared with the reference geometry obtained at the CCSD level of theory. SCS-MP2 reproduces best the reference geometry of (Me 3 SnCN) 2 and its accuracy is close to that of the MP4 (SDQ) method. Two families of basis sets, namely the correlation-consistent basis sets proposed by Dunning and co-workers and the 'def2' basis sets developed by Ahlrichs and co-workers, are taken into account and their effect on the geometry of the dimer is examined in detail. The intermolecular interaction in (Me 3 SnCN) 2 has been analyzed using SAPT, NBO, QTAIM, and ELF. The results indicate that the (Me 3 SnCN) 2 dimer possesses a weak N → Sn coordination bond whose character is predominantly ionic. A value of −7.64 kcal/mol is proposed to be the best estimate of the interaction energy between the Me 3 SnCN molecules in the dimer.

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Theoretical interpretation of Grimme’s spin-component-scaled second order Møller-Plesset theory

Abstract: It is shown that spin-component-scaled second order Møller-Plesset theory proposed by Grimme [J. Chem. Phys. 118, 9095 (2003)] can be interpreted as a two-parameter scaling of the zero order Hamiltonian, a generalization of the approach reported by Feenberg [Phys. Rev. 103, 1116 (1956)].

Cited by 98 publications

References 45 publications

Theoretical Thermodynamics for Large Molecules: Walking the Thin Line between Accuracy and Computational Cost

Theoretical Thermodynamics for Large Molecules: Walking the Thin Line between Accuracy and Computational Cost

Scaled MP3 Non‐Covalent Interaction Energies Agree Closely with Accurate CCSD(T) Benchmark Data

Theoretical investigation of the N → Sn coordination in (Me3SnCN)2

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