title: Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules.
abstract: In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Mo̸ller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H4)3P}2(C6H5)Pt(C≡C)4Pt(C6H5){(p-CH3C6H4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.
authors.affiliation: Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan.
authors.forename: Junji
authors.initials: J
authors.lastname: Seino
authors.forename: Hiromi
authors.initials: H
authors.lastname: Nakai