A parallel algorithm is described for the coupled-cluster singles and doubles method augmented with a perturbative correction for triple excitations CCSD(T) using the resolution-of-the-identity (RI) ...approximation for two-electron repulsion integrals (ERIs). The algorithm bypasses the storage of four-center ERIs by adopting an integral-direct strategy. The CCSD amplitude equations are given in a compact quasi-linear form by factorizing them in terms of amplitude-dressed three-center intermediates. A hybrid MPI/OpenMP parallelization scheme is employed, which uses the OpenMP-based shared memory model for intranode parallelization and the MPI-based distributed memory model for internode parallelization. Parallel efficiency has been optimized for all terms in the CCSD amplitude equations. Two different algorithms have been implemented for the rate-limiting terms in the CCSD amplitude equations that entail O ( N O 2 N V 4 ) and O ( N O 3 N V 3 ) -scaling computational costs, where N O and N V denote the number of correlated occupied and virtual orbitals, respectively. One of the algorithms assembles the four-center ERIs requiring N V 4 and N O 2 N V 2-scaling memory costs in a distributed manner on a number of MPI ranks, while the other algorithm completely bypasses the assembling of quartic memory-scaling ERIs and thus largely reduces the memory demand. It is demonstrated that the former memory-expensive algorithm is faster on a few hundred cores, while the latter memory-economic algorithm shows a better strong scaling in the limit of a few thousand cores. The program is shown to exhibit a near-linear scaling, in particular for the compute-intensive triples correction step, on up to 8000 cores. The performance of the program is demonstrated via calculations involving molecules with 24–51 atoms and up to 1624 atomic basis functions. As the first application, the complete basis set (CBS) limit for the interaction energy of the π-stacked uracil dimer from the S66 data set has been investigated. This work reports the first calculation of the interaction energy at the CCSD(T)/aug-cc-pVQZ level without local orbital approximation. The CBS limit for the CCSD correlation contribution to the interaction energy was found to be −8.01 kcal/mol, which agrees very well with the value −7.99 kcal/mol reported by Schmitz, Hättig, and Tew Phys. Chem. Chem. Phys. 2014, 16, 22167−22178 . The CBS limit for the total interaction energy was estimated to be −9.64 kcal/mol.
The bonding structures of the ground state and the lowest five excited states of rhodium monoboride are identified by determining the quasi-atomic orbitals in full valence space MCSCF wave functions ...and the interactions between these orbitals. A quadruple bond, namely two π-bonds and two σ-bonds, is identified and characterized for the X1Σ+ ground state, in agreement with a previous report ( Cheung J. Phys. Chem. Lett. 2020, 11, 659−663 ). However, in all excited states, the bonding is predicted to be weaker because, in these states, one of the σ-bonding interactions has a small magnitude. In the a3Δ and A1Δ states, the bond order is between a triple and quadruple bond. In the b3Σ+ state, the Rh–B linkage is a triple bond. In the c3Π and B1Π states, the atoms are linked by a double bond due to an additional weakening of the two π-bonds. The decreases in the predicted bond strengths are reflected in the decreases of the predicted binding energies and in the increases of the predicted bond lengths from the X1Σ+ ground state to the c3Π and the B1Π excited states. Notably, the 5pσ orbital of rhodium, which is vacant in the ground state of the atom, plays a significant role in the molecule.
Many-Body Dispersion Xu, Peng; Alkan, Melisa; Gordon, Mark S
Chemical reviews,
11/2020, Letnik:
120, Številka:
22
Journal Article
Recenzirano
A broad range of approaches to many-body dispersion are discussed, including empirical approaches with multiple fitted parameters, augmented density functional-based approaches, symmetry adapted ...perturbation theory, and a supermolecule approach based on coupled cluster theory. Differing definitions of “body” are considered, specifically atom-based vs molecule-based approaches.
An algorithm is presented for the coupled-cluster singles, doubles, and perturbative triples correction CCSD(T) method based on the density fitting or the resolution-of-the-identity (RI) ...approximation for performing calculations on heterogeneous computing platforms composed of multicore CPUs and graphics processing units (GPUs). The directive-based approach to GPU offloading offered by the OpenMP application programming interface has been employed to adapt the most compute-intensive terms in the RI-CCSD amplitude equations with computational costs scaling as O ( N O 2 N V 4 ) , O ( N O 3 N V 3 ) , and O ( N O 4 N V 2 ) (where N O and N V denote the numbers of correlated occupied and virtual orbitals, respectively) and the perturbative triples correction to execute on GPU architectures. The pertinent tensor contractions are performed using an accelerated math library such as cuBLAS or hipBLAS. Optimal strategies are discussed for splitting large data arrays into tiles to fit them into the relatively small memory space of the GPUs, while also minimizing the low-bandwidth CPU–GPU data transfers. The performance of the hybrid CPU–GPU RI-CCSD(T) code is demonstrated on pre-exascale supercomputers composed of heterogeneous nodes equipped with NVIDIA Tesla V100 and A100 GPUs and on the world’s first exascale supercomputer named “Frontier”, the nodes of which consist of AMD MI250X GPUs. Speedups within the range 4–8× relative to the recently reported CPU-only algorithm are obtained for the GPU-offloaded terms in the RI-CCSD amplitude equations. Applications to polycyclic aromatic hydrocarbons containing 16–66 carbon atoms demonstrate that the acceleration of the hybrid CPU–GPU code for the perturbative triples correction relative to the CPU-only code increases with the molecule size, attaining a speedup of 5.7× for the largest circumovalene molecule (C66H20). The GPU-offloaded code enables the computation of the perturbative triples correction for the C60 molecule using the cc-pVDZ/aug-cc-pVTZ-RI basis sets in 7 min on Frontier when using 12,288 AMD GPUs with a parallel efficiency of 83.1%.
The photoisomerization process of 1,2-diphenylethylene (stilbene) is investigated using the spin-flip density functional theory (SFDFT), which has recently been shown to be a promising approach for ...locating conical intersection (CI) points (Minezawa, N.; Gordon, M. S. J. Phys. Chem. A 2009, 113, 12749). The SFDFT method gives valuable insight into twisted stilbene to which the linear response time-dependent DFT approach cannot be applied. In contrast to the previous SFDFT study of ethylene, a distinct twisted minimum is found for stilbene. The optimized structure has a sizable pyramidalization angle and strong ionic character, indicating that a purely twisted geometry is not a true minimum. In addition, the SFDFT approach can successfully locate two CI points: the twisted-pyramidalized CI that is similar to the ethylene counterpart and another CI that possibly lies on the cyclization pathway of cis-stilbene. The mechanisms of the cis–trans isomerization reaction are discussed on the basis of the two-dimensional potential energy surface along the twisting and pyramidalization angles.
A new, general spin-correct spin-flip configuration interaction (SF-CI) method is introduced by extending the occupation restricted multiple active spaces (ORMAS) CI method in GAMESS. SF-ORMAS is a ...single reference CI method that utilizes a high-spin restricted open shell determinant on which an arbitrary amount of spin-flipped excitations are carried out to generate a wave function of desired multiplicity. Furthermore, the SF-ORMAS method allows for a flexible design of the active space(s) to fit the chemical problem at hand. Therefore, a variety of spin-flip schemes can be implemented within this one formalism. As SF-ORMAS mostly accounts for static correlation, dynamic correlation is included through perturbation theory. The new method is demonstrated for single and multiple bond breaking, diradical systems, vertical excitations of linear alkenes, and the singlet-triplet energy gap of silicon trimer.
A new spin-complete spin-flip configuration interaction (SF-CI) method was developed using the ORMAS-CI algorithm, along with a perturbative correction for capturing dynamic and non-dynamic correlation.
An interface between ab initio quantum mechanics (QM) methods and the general effective fragment potential (EFP2) method, QM-EFP2, is implemented in which the intermolecular interactions between a QM ...molecule and EFP fragments consist of Coulomb, polarization, exchange repulsion (exrep), and dispersion components. In order to ensure accuracy in the QM-EFP2 exrep interaction energy, the EFP2-EFP2 spherical Gaussian overlap (SGO) approximation is abandoned and replaced with the exact electron repulsion integrals (ERI) that are evaluated with a direct method to reduce disk usage. A Gaussian damping function for the QM-EFP2 Coulomb component damps both the EFP nuclear and electronic charges. A new overlap damping function has been implemented for the QM-EFP2 dispersion component. The current QM-EFP2 implementation has been benchmarked with the S22 and S66 data sets and demonstrates excellent agreement with symmetry-adapted perturbation theory (SAPT) for component energies and with coupled cluster theory CCSD(T) for the total interaction energies. Water clusters of various sizes (up to 256 water molecules) have been tested; it is shown that the QM-EFP2 method has an accuracy that is comparable to that of EFP2-EFP2. It has been shown previously that the accuracy of EFP2-EFP2 intermolecular interactions is comparable to that of second-order perturbation theory (MP2) or better. The implementation of the distributed data interface (DDI) parallelization scheme significantly improves the efficiency of QM-EFP2 calculations. The time to form the QM-EFP2 Fock operator per SCF iteration for water clusters scales linearly with the number EFP basis functions.
Many-Body Dispersion in Molecular Clusters Alkan, Melisa; Xu, Peng; Gordon, Mark S
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory,
10/2019, Letnik:
123, Številka:
39
Journal Article
Recenzirano
Many-body dispersion has gained considerable attention over the past decade, particularly for condensed phase systems. However, quantitatively accurate studies of many-body dispersion have only ...recently become feasible due to challenges in reliability and accuracy. Currently available methodologies for calculating many-body dispersion have been challenged, with recent evidence suggesting, for example, that dispersion-corrected density functional theory (DFT) schemes cannot consistently predict many-body dispersion accurately. This study evaluates many-body dispersion energies using a composite approach that employs singles and doubles coupled cluster theory with perturbative/noniterative triples, CCSD(T), combined with an extrapolation to the complete basis set (CBS) limit. The combined CCSD(T)/CBS approach is applied to Ar n and (H2O) n , n = 3–10, clusters, and a new data set called S22(3), which includes trimers generated based on the S22 data set. In these systems, the many-body dispersion provides a very small contribution to the total interaction energy of all of the systems studied, generally 3% or less of the total interaction energy. Two-body dispersion is the dominant dispersion contribution and many-body dispersion contributes no more than 5.7% of the total dispersion energy, generally staying below 2%.
