RESUMEN
In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group, we focused on the tailored coupled cluster (TCC) approach. This method works well in many situations; however, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias toward the reference determinant representing the Fermi vacuum. Although sometimes it is possible to use a compensation scheme to avoid this bias for energy differences, it is certainly a drawback. In order to overcome this bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have implemented and compared the performance of three Hilbert-space multireference coupled cluster (MRCC) variants-the state universal one and the Brillouin-Wigner and Mukherjee's state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethyleneethane molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. We have also investigated the sensitivity of the results on the orbital rotation of the highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.
RESUMEN
We present, to the best of our knowledge, the first attempt to exploit the super-computer platform for quantum chemical density matrix renormalization group (QC-DMRG) calculations. We have developed the parallel scheme based on the in-house MPI global memory library, which combines operator and symmetry sector parallelisms, and tested its performance on three different molecules, all typical candidates for QC-DMRG calculations. In case of the largest calculation, which is the nitrogenase FeMo cofactor cluster with the active space comprising 113 electrons in 76 orbitals and bond dimension equal to 6000, our parallel approach scales up to approximately 2000 CPU cores.
RESUMEN
There are three essential problems in computational relativistic chemistry: Electrons moving at relativistic speeds, close lying states, and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules in which all the three effects are present. These are the heavier transition metal compounds, lanthanides, and actinides with open d or f shells. For such systems, sufficiently accurate numerical methods are not available, which hinders the application of theoretical chemistry in this field. In this paper, we combine two numerical methods in order to address this challenging class of molecules. These are the relativistic versions of coupled cluster methods and the density matrix renormalization group (DMRG) method. To the best of our knowledge, this is the first relativistic implementation of the coupled cluster method externally corrected by DMRG. The method brings a significant reduction of computational costs as we demonstrate on the system of TlH, AsH, and SbH.
RESUMEN
We present a new implementation of density matrix renormalization group based tailored coupled clusters method (TCCSD), which employs the domain-based local pair natural orbital approach (DLPNO). Compared to the previous local pair natural orbital (LPNO) version of the method, the new implementation is more accurate, offers more favorable scaling, and provides more consistent behavior across the variety of systems. On top of the singles and doubles, we include the perturbative triples correction (T), which is able to retrieve even more dynamic correlation. The methods were tested on three systems: tetramethyleneethane, oxo-Mn(Salen), and iron(II)-porphyrin model. The first two were revisited to assess the performance with respect to LPNO-TCCSD. For oxo-Mn(Salen), we retrieved between 99.8 and 99.9% of the total canonical correlation energy which is an improvement of 0.2% over the LPNO version in less than 63% of the total LPNO runtime. Similar results were obtained for iron(II)-porphyrin. When the perturbative triples correction was employed, irrespective of the active space size or system, the obtained energy differences between two spin states were within the chemical accuracy of 1 kcal/mol using the default DLPNO settings.
RESUMEN
Recently, the correlation theory of the chemical bond was developed, which applies concepts of quantum information theory for the characterization of chemical bonds, based on the multiorbital correlations within the molecule. Here, for the first time, we extend the use of this mathematical toolbox for the description of electron-deficient bonds. We start by verifying the theory on the textbook example of a molecule with three-center two-electron bonds, namely, diborane(6). We then show that the correlation theory of the chemical bond is able to properly describe the bonding situation in more exotic molecules which have been synthesized and characterized only recently, in particular, the diborane molecule with four hydrogen atoms [diborane(4)] and a neutral zerovalent s-block beryllium complex, whose surprising stability was attributed to a strong three-center two-electron π bond stretching across the C-Be-C core. Our approach is of high importance especially in the light of a constant chase after novel compounds with extraordinary properties where the bonding is expected to be unusual.