Accuracy of DLPNO–CCSD(T) Method for Noncovalent Bond Dissociation Enthalpies from Coinage Metal Cation Complexes

Abstract

Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms. KAUST Repository IntroductionComputational chemistry is routinely applied nowadays to support and integrate experimental studies in transition-metal catalysis. [1][2][3][4][5][6][7] The successful standalone experimental-free theoretical predictions in this field are far less common, however. 8 While some failures in theoretical predictions are originated from the complexity of the systems themselves and can be ameliorated by proper inclusion of the effects deriving from incomplete sampling of the conformational space and/or solvation, 1,9 the other failures are related to the accuracy of electronic structure methods. In general, scalar/vector relativistic effects, basis set completeness and multireference character of some systems should be properly addressed regardless on the electronic structure method used. [10][11] When it comes specifically to density functional theory (DFT) methods, which is the only affordable computational protocol to study systems of "realistic-size", one has to remember that the performance of the underlying exchange-correlation (XC) functionals is not uniform, and provides low to high accuracy predictions depending on the chemical system under study. 12 The careful "calibration" against highly accurate experimental measurements or wave On the other hand, so-called "ab initio" WFT methods 28 are rigorous and allow to systematic...

On the Accuracy of Density Functional Theory in Zeolite Catalysis

“…[93,94] For this cluster size, one can furthermore use canonical, 2 nd -order Møller-Plesset perturbation theory (MP2) with the def2-TZVPP basis set. Additionally, non-canonical coupled cluster methods such as the DLPNO-CCSD(T) approach [95][96][97][98] can be used employing the def2-TZVPP basis set as implemented in the Orca program.…”

“…Single points were also performed with the hybrid functionals PBE0-D3 [108] , B3LYP-D3 [126][127] and M06 [109] and Møller-Plesset second order perturbation theory MP2 [128][129][130] in Turbomole all with the def2-TZVPP/def2-QZVPP basis sets and a corresponding auxiliary basis set [131][132][133] . For CCSD(T) [129][130] both Turbomole and Orca program packages were used, Turbomole for canonical CCSD(T) calculations and Orca [93][94] to compare the accuracy of the DLPNO approximation [97][98] with the canonical values obtained for the smallest cluster model T1. Then, DLPNO CCSD(T) was carried out for the largest cluster and canonical CCSD for T1 with cc-pVXZ [134] (X=D, T, Q) basis-sets, for complete basis-set limit extrapolation (CBS) [98,[101][102]135] (details on the equations used available in the SI).…”

The divide–expand–consolidate coupled cluster scheme

“…While the PAO basis allows for significant reductions in terms of the number of CC amplitudes to consider, the virtual parameter space may be further compressed using pair natural orbitals (PNOs), which are constructed from (an approximation to) the MP2 correlation density matrix for each electron pair. For example, the domain‐based local PNO (DLPNO) CCSD(T) method has been used successfully for many applications within computational chemistry . Local CC methods relying on orbital‐specific virtuals (OSVs) have also been developed and are closely related to PNOs.…”

“…Local CC methods relying on orbital‐specific virtuals (OSVs) have also been developed and are closely related to PNOs. Finally, we note that the combination of wave‐function based local CC approximations with explicit correlation techniques has lead to important improvements by reducing both basis set errors and domain errors …”

Superhalogen and Superacid

“…[23] This method was shown to provide results of canonical coupled cluster quality. [24][25][26][27][28][29][30] All the calculations were performed for gas phase.…”