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Using the analytic derivatives approach, dipole moments of high-level density-fitted coupled-cluster (CC) methods, such as coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)], are presented. To obtain the high accuracy results, the computed dipole moments are extrapolated to the complete basis set (CBS) limits applying focal-point approximations. Dipole moments of the CC methods considered are compared with the experimental gas-phase values, as well as with the common DFT functionals, such as B3LYP, BP86, M06-2X, and BLYP. For all test sets considered, the CCSD(T) method provides substantial improvements over Hartree-Fock (HF), by 0.076-0.213 D, and its mean absolute errors are lower than 0.06 D. Furthermore, our results indicate that even though the performances of the common DFT functionals considered are significantly better than that of HF, their results are not comparable with the CC methods. Our results demonstrate that the CCSD(T)/CBS level of theory provides highly-accurate dipole moments, and its quality approaching the experimental results. © 2019 Wiley Periodicals, Inc.
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A catalytic aza-Nazarov cyclization between 3,4-dihydroisoquinolines and α,ß-unsaturated acyl chlorides has been developed to access α-methylene-γ-lactam products in good yields (up to 79%) as single diastereomers. The reactions proceed efficiently when AgOTf is used as an anion exchange catalyst with a 20 mol % loading at 80 °C. Computational studies were performed to investigate the reaction mechanism, and the findings support the role of the -TMS group in reducing the reaction barrier of the key cyclization step.
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Drawing upon a consecutive amide coupling and intramolecular cyclisation pathway, a one-pot, straightforward synthetic route has been developed for a range of pyrazole fused γ-pyrone derivatives. The reaction mechanism proposed for the chemoselective formation of γ-pyranopyrazole is furthermore fully supported by experimental and computational studies.
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An assessment of orbital-optimized MP2.5 (OMP2.5) [ Bozkaya, U.; Sherrill, C. D. J. Chem. Phys. 2014, 141, 204105 ] for thermochemistry and kinetics is presented. The OMP2.5 method is applied to closed- and open-shell reaction energies, barrier heights, and aromatic bond dissociation energies. The performance of OMP2.5 is compared with that of the MP2, OMP2, MP2.5, MP3, OMP3, CCSD, and CCSD(T) methods. For most of the test sets, the OMP2.5 method performs better than MP2.5 and CCSD, and provides accurate results. For barrier heights of radical reactions and aromatic bond dissociation energies OMP2.5-MP2.5, OMP2-MP2, and OMP3-MP3 differences become obvious. Especially, for aromatic bond dissociation energies, standard perturbation theory (MP) approaches dramatically fail, providing mean absolute errors (MAEs) of 22.5 (MP2), 17.7 (MP2.5), and 12.8 (MP3) kcal mol(-1), while the MAE values of the orbital-optimized counterparts are 2.7, 2.4, and 2.4 kcal mol(-1), respectively. Hence, there are 5-8-folds reductions in errors when optimized orbitals are employed. Our results demonstrate that standard MP approaches dramatically fail when the reference wave function suffers from the spin-contamination problem. On the other hand, the OMP2.5 method can reduce spin-contamination in the unrestricted Hartree-Fock (UHF) initial guess orbitals. For overall evaluation, we conclude that the OMP2.5 method is very helpful not only for challenging open-shell systems and transition-states but also for closed-shell molecules. Hence, one may prefer OMP2.5 over MP2.5 and CCSD as an O(N(6)) method, where N is the number of basis functions, for thermochemistry and kinetics. The cost of the OMP2.5 method is comparable with that of CCSD for energy computations. However, for analytic gradient computations, the OMP2.5 method is only half as expensive as CCSD.
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An assessment of the orbital-optimized coupled-electron pair theory [or simply "optimized CEPA(0)," OCEPA(0)] [Bozkaya and Sherrill, J. Chem. Phys. 2013, 139, 054104] for thermochemistry and kinetics is presented. The OCEPA(0) method is applied to closed- and open-shell reaction energies, barrier heights, and radical stabilization energies (RSEs). The performance of OCEPA(0) is compared with those of the MP2, CEPA(0), OCEPA(0), CEPA(1), coupled-cluster singles and doubles (CCSD), and CCSD(T) methods [at complete basis set limits employing cc-pVTZ and cc-pVQZ basis sets]. For the most of the test sets, the OCEPA(0) method performs better than CEPA(0), CEPA(1), and CCSD, and provides accurate results. Especially, for open-shell reaction energies and barrier heights, the OCEPA(0)-CEPA(1) and OCEPA(0)-CCSD differences become obvious. Similarly, for barrier heights and RSEs, the OCEPA(0) method improves on CEPA(0) by 1.6 and 2.3 kcal mol(-1) . Our results demonstrate that the CEPA(0) method dramatically fails when the reference wave function suffers from the spin-contamination problem. Conversely, the OCEPA(0) method can annihilate spin-contamination in the unrestricted-Hartree-Fock initial guess orbitals and can yield stable solutions. For overall evaluation, we conclude that the OCEPA(0) method is quite helpful not only for problematic open-shell systems and transition-states but also for closed-shell molecules. Hence, one may prefer OCEPA(0) over CEPA(0), CEPA(1), and CCSD as an O(N6) method, where N is the number of basis functions, for thermochemistry and kinetics. As discussed previously, the cost of the OCEPA(0) method is as much as of CCSD and CEPA(1) for energy computations. However, for analytic gradient computations, the OCEPA(0) method is two times less expensive than CCSD and CEPA(1). Further, the stationary properties of the OCEPA(0) method making it promising for excited state properties via linear response theory.
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The accurate description of noncovalent interactions is one of the most challenging problems in modern computational chemistry, especially those for open-shell systems. In this study, an investigation of open-shell noncovalent interactions with the orbital-optimized MP2 and MP3 (OMP2 and OMP3) is presented. For the considered test set of 23 complexes, mean absolute errors in noncovalent interaction energies (with respect to CCSD(T) at complete basis set limits) are 0.68 (MP2), 0.37 (OMP2), 0.59 (MP3), 0.23 (OMP3), and 0.38 (CCSD) kcal mol(-1) . Hence, with a greatly reduced computational cost, one may achieve CCSD quality at the MP2 level by orbital optimization [scaling formally as O(N(6)) for CCSD compared to O(N(5)) for OMP2, where N is the number of basis functions]. Further, one may obtain a considerably better performance than CCSD using the OMP3 method, which has also a lower cost than CCSD.
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An assessment of the OMP3 method and its spin-component and spin-scaled variants for thermochemistry and kinetics is presented. For reaction energies of closed-shell systems, the CCSD, SCS-MP3, and SCS-OMP3 methods show better performances than other considered methods, and no significant improvement is observed due to orbital optimization. For barrier heights, OMP3 and SCS-OMP3 provide the lowest mean absolute deviations. The MP3 method yields considerably higher errors, and the spin scaling approaches do not help to improve upon MP3, but worsen it. For radical stabilization energies, the CCSD, OMP3, and SCS-OMP3 methods exhibit noticeably better performances than MP3 and its variants. Our results demonstrate that if the reference wave function suffers from a spin-contamination, then the MP3 methods dramatically fail. On the other hand, the OMP3 method and its variants can tolerate the spin-contamination in the reference wave function. For overall evaluation, we conclude that OMP3 is quite helpful, especially in electronically challenged systems, such as free radicals or transition states where spin contamination dramatically deteriorates the quality of the canonical MP3 and SCS-MP3 methods. Both OMP3 and CCSD methods scale as n(6), where n is the number of basis functions. However, the OMP3 method generally converges in much fewer iterations than CCSD. In practice, OMP3 is several times faster than CCSD in energy computations. Further, the stationary properties of OMP3 make it much more favorable than CCSD in the evaluation of analytic derivatives. For OMP3, the analytic gradient computations are much less expensive than CCSD. For the frequency computation, both methods require the evaluation of the perturbed amplitudes and orbitals. However, in the OMP3 case there is still a significant computational time savings due to simplifications in the analytic Hessian expression owing to the stationary property of OMP3. Hence, the OMP3 method emerges as a very useful tool for computational quantum chemistry.