We present a four-component relativistic unitary coupled cluster method for atoms and molecules. We have used commutator-based non-perturbative approximation using the "Bernoulli expansion" to derive an approximation to the relativistic unitary coupled cluster method. The performance of the full quadratic unitary coupled-cluster singles and doubles method (qUCCSD), as well as a perturbative approximation variant (UCC3), has been reported for both energies and properties. It can be seen that both methods give results comparable to those of the standard relativistic coupled cluster method. The qUCCSD method shows better agreement with experimental results due to the better inclusion of relaxation effects. The relativistic UCC3 and qUCCSD methods can simulate the spin-forbidden transition with easy access to transition properties. A natural spinor-based scheme to reduce the computational cost of relativistic UCC3 and qUCCSD methods has been discussed.
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http://dx.doi.org/10.1063/5.0207091 | DOI Listing |
J Chem Inf Model
January 2025
Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
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View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Earth and Environmental Science, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, USA.
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View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
X-ray absorption spectroscopy (XAS) is a powerful method for exploring molecular electronic structure by exciting core electrons into higher unoccupied molecular orbitals. In this study, we present the first integration of the spin-unrestricted similarity-transformed equation-of-motion coupled cluster method (CVS-USTEOM-CCSD) for core-excited and core-ionized states into the ORCA quantum chemistry package. Using the core-valence separation (CVS) approach, we evaluate the accuracy of CVS-USTEOM-CCSD across 13 open-shell organic systems, covering over 20 core excitations with diverse spin multiplicities (doublet, triplet, and quartet).
View Article and Find Full Text PDFLangmuir
January 2025
Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013, China.
Cavitation has been a hot research topic for scholars in various fields because of the intense mechanical, chemical, and thermal effects of bubble collapse. It forms a cluster of bubbles, and the bubbles will affect, interfere with, and couple with each other. To grasp the main factors affecting bubble collapse and the interbubble mechanism, the paper adopts the molecular dynamics simulation combined with the coarse-grained force field to study the collapse process of the double bubble model and takes the dynamic shape change of the bubbles, the local velocity distribution, and the local pressure distribution as the object to summarize the position angle, the shock velocity, and the bubble distance on the collapse law and the primary and secondary influence relationship and then reveals the interbubble mechanism.
View Article and Find Full Text PDFBMC Health Serv Res
January 2025
Department of Public Health Policy and Systems, University of Liverpool, Brownlow Street, Liverpool, L69 3GF, UK.
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