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Journal ArticleDOI

Development and Validation of a Parameter-Free Model Chemistry for the Computation of Reliable Reaction Rates.

06 Jul 2021-Journal of Chemical Theory and Computation (American Chemical Society (ACS))-Vol. 17, Iss: 8, pp 4913-4928
TL;DR: In this paper, a recently developed model chemistry (jun-cheap) has been modified and proposed as an effective, reliable, and parameter-free scheme for the computation of accurate reaction rates with special reference to astrochemical and atmospheric processes.
Abstract: A recently developed model chemistry (jun-Cheap) has been slightly modified and proposed as an effective, reliable, and parameter-free scheme for the computation of accurate reaction rates with special reference to astrochemical and atmospheric processes. Benchmarks with different sets of state-of-the-art energy barriers spanning a wide range of values show that, in the absence of strong multireference contributions, the proposed model outperforms the most well-known model chemistries, reaching a subchemical accuracy without any empirical parameter and with affordable computer times. Some test cases show that geometries, energy barriers, zero point energies, and thermal contributions computed at this level can be used in the framework of the master equation approach based on the ab initio transition-state theory for obtaining accurate reaction rates.
Citations
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Journal ArticleDOI
TL;DR: The history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners as discussed by the authors .
Abstract: In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

38 citations

Journal ArticleDOI
TL;DR: In this article, the authors further enlarged the compilation of available semi-experimental (SE) equilibrium structures, now covering the most important fragments containing H, B, C, N, O, F, P, S, and Cl atoms collected in the new SE100 database.
Abstract: The determination of accurate equilibrium molecular structures plays a fundamental role for understanding many physical-chemical properties of molecules, ranging from the precise evaluation of the electronic structure to the analysis of the role played by dynamical and environmental effects in tuning their overall behavior. For small semi-rigid systems in the gas phase, state-of-the-art quantum chemical computations rival the most sophisticated experimental (from, for example, high-resolution spectroscopy) results. For larger molecules, more effective computational approaches must be devised. To this end, we have further enlarged the compilation of available semi-experimental (SE) equilibrium structures, now covering the most important fragments containing H, B, C, N, O, F, P, S, and Cl atoms collected in the new SE100 database. Next, comparison with geometries optimized by methods rooted in the density functional theory showed that the already remarkable results delivered by PW6B95 and, especially, rev-DSDPBEP86 functionals can be further improved by a linear regression (LR) approach. Use of template fragments (taken from the SE100 library) together with LR estimates for the missing interfragment parameters paves the route toward accurate structures of large molecules, as witnessed by the very small deviations between computed and experimental rotational constants. The whole approach has been implemented in a user-friendly tool, termed nano-LEGO, and applied to a number of demanding case studies.

29 citations

Journal ArticleDOI
TL;DR: In this paper, a family of effective, reliable, and parameter-free schemes for the computation of accurate interaction energies of molecular complexes ruled by noncovalent interactions is proposed, which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries.
Abstract: A recently developed model chemistry (denoted as junChS [Alessandrini, S.; et al. J. Chem. Theory Comput.2020,16, 988-1006]) has been extended to the employment of explicitly correlated (F12) methods. This led us to propose a family of effective, reliable, and parameter-free schemes for the computation of accurate interaction energies of molecular complexes ruled by noncovalent interactions. A thorough benchmark based on a wide range of interactions showed that the so-called junChS-F12 model, which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries, has an improved performance with respect to its conventional counterpart and outperforms well-known model chemistries. Without employing any empirical parameter and at an affordable computational cost, junChS-F12 reaches subchemical accuracy. Accurate characterizations of molecular complexes are usually limited to energetics. To take a step forward, the conventional and F12 composite schemes developed for interaction energies have been extended to structural determinations. A benchmark study demonstrated that the most effective option is to add MP2-F12 core-valence correlation corrections to fc-CCSD(T)-F12/jun-cc-pVTZ geometries without the need of recovering the basis set superposition error and the extrapolation to the complete basis set.

16 citations

Journal ArticleDOI
TL;DR: In this article , the authors used composite post-Hartree-Fock schemes and hybrid coupled-cluster/density functional theory approaches to predict the structural and ro-vibrational spectroscopic properties of the different conformers within the framework of the second-order vibrational perturbation theory.
Abstract: The first step to shed light on the abiotic synthesis of biochemical building blocks, and their further evolution toward biological systems, is the detection of the relevant species in astronomical environments, including earthlike planets. To this end, the species of interest need to be accurately characterized from structural, energetic, and spectroscopic viewpoints. This task is particularly challenging when dealing with flexible systems, whose spectroscopic signature is ruled by the interplay of small- and large-amplitude motions (SAMs and LAMs, respectively) and is further tuned by the conformational equilibrium. In such instances, quantum chemical (QC) calculations represent an invaluable tool for assisting the interpretation of laboratory measurements or even observations. In the present work, the role of QC results is illustrated with reference to glycolic acid (CH2OHCOOH), a molecule involved in photosynthesis and plant respiration and a precursor of oxalate in humans, which has been detected in the Murchison meteorite but not yet in the interstellar medium or in planetary atmospheres. In particular, the equilibrium structure of the lowest-energy conformer is derived by employing the so-called semiexperimental approach. Then, accurate yet cost-effective QC calculations relying on composite post-Hartree–Fock schemes and hybrid coupled-cluster/density functional theory approaches are used to predict the structural and ro-vibrational spectroscopic properties of the different conformers within the framework of the second-order vibrational perturbation theory. A purposely tailored discrete variable representation anharmonic approach is used to treat the LAMs related to internal rotations. The computed spectroscopic data, particularly those in the infrared region, complement the available experimental investigations, thus enhancing the possibility of an astronomical detection of this molecule.

10 citations

Journal ArticleDOI
TL;DR: The 1:1 benzofuran-formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups.
Abstract: The 1:1 benzofuran-formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint "rotational spectroscopy-quantum chemistry" strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low-energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone-pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi-experimental equilibrium structure for a molecular complex of such a dimension.

9 citations

References
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Journal ArticleDOI
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
Abstract: In the past, basis sets for use in correlated molecular calculations have largely been taken from single configuration calculations. Recently, Almlof, Taylor, and co‐workers have found that basis sets of natural orbitals derived from correlated atomic calculations (ANOs) provide an excellent description of molecular correlation effects. We report here a careful study of correlation effects in the oxygen atom, establishing that compact sets of primitive Gaussian functions effectively and efficiently describe correlation effects i f the exponents of the functions are optimized in atomic correlated calculations, although the primitive (s p) functions for describing correlation effects can be taken from atomic Hartree–Fock calculations i f the appropriate primitive set is used. Test calculations on oxygen‐containing molecules indicate that these primitive basis sets describe molecular correlation effects as well as the ANO sets of Almlof and Taylor. Guided by the calculations on oxygen, basis sets for use in correlated atomic and molecular calculations were developed for all of the first row atoms from boron through neon and for hydrogen. As in the oxygen atom calculations, it was found that the incremental energy lowerings due to the addition of correlating functions fall into distinct groups. This leads to the concept of c o r r e l a t i o n c o n s i s t e n t b a s i s s e t s, i.e., sets which include all functions in a given group as well as all functions in any higher groups. Correlation consistent sets are given for all of the atoms considered. The most accurate sets determined in this way, [5s4p3d2f1g], consistently yield 99% of the correlation energy obtained with the corresponding ANO sets, even though the latter contains 50% more primitive functions and twice as many primitive polarization functions. It is estimated that this set yields 94%–97% of the total (HF+1+2) correlation energy for the atoms neon through boron.

26,705 citations

Journal ArticleDOI
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.
Abstract: A perturbation theory is developed for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation. It is shown by this development that the first order correction for the energy and the charge density of the system is zero. The expression for the second-order correction for the energy greatly simplifies because of the special property of the zero-order solution. It is pointed out that the development of the higher approximation involves only calculations based on a definite one-body problem.

12,067 citations

Journal ArticleDOI
TL;DR: In this paper, a new augmented version of coupled-cluster theory, denoted as CCSD(T), is proposed to remedy some of the deficiencies of previous augmented coupledcluster models.

7,249 citations

Book
01 Jan 1965

5,302 citations

Journal ArticleDOI
TL;DR: The uniformity with which B2-PLYP improves for a wide range of chemical systems emphasizes the need of (virtual) orbital-dependent terms that describe nonlocal electron correlation in accurate exchange-correlation functionals.
Abstract: A new hybrid density functional for general chemistry applications is proposed. It is based on a mixing of standard generalized gradient approximations GGAs for exchange by Becke B and for correlation by Lee, Yang, and Parr LYP with Hartree-Fock HF exchange and a perturbative second-order correlation part PT2 that is obtained from the Kohn-Sham GGA orbitals and eigenvalues. This virtual orbital-dependent functional contains only two global parameters that describe the mixture of HF and GGA exchange ax and of the PT2 and GGA correlation c, respectively. The parameters are obtained in a least-squares-fit procedure to the G2/97 set of heat of formations. Opposed to conventional hybrid functionals, the optimum ax is found to be quite large 53% with c=27% which at least in part explains the success for many problematic molecular systems compared to conventional approaches. The performance of the new functional termed B2-PLYP is assessed by the G2/97 standard benchmark set, a second test suite of atoms, molecules, and reactions that are considered as electronically very difficult including transition-metal compounds, weakly bonded complexes, and reaction barriers and comparisons with other hybrid functionals of GGA and meta-GGA types. According to many realistic tests, B2-PLYP can be regarded as the best general purpose density functional for molecules e.g., a mean absolute deviation for the two test sets of only 1.8 and 3.2 kcal/mol compared to about 3 and 5 kcal/mol, respectively, for the best other density functionals. Very importantly, also the maximum and minium errors outliers are strongly reduced by about 10‐20 kcal/mol. Furthermore, very good results are obtained for transition state barriers but unlike previous attempts at such a good description, this definitely comes not at the expense of equilibrium properties. Preliminary calculations of the equilibrium bond lengths and harmonic vibrational frequencies for diatomic molecules and transition-metal complexes also show very promising results. The uniformity with which B2-PLYP improves for a wide range of chemical systems emphasizes the need of virtual orbital-dependent terms that describe nonlocal electron correlation in accurate exchange-correlation functionals. From a practical point of view, the new functional seems to be very robust and it is thus suggested as an efficient quantum chemical method of general purpose. © 2006 American Institute of Physics. DOI: 10.1063/1.2148954

2,704 citations