Density-matrix renormalization-group algorithms with nonorthogonal orbitals and non-Hermitian operators, and applications to polyenes
- Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853-1301 (United States)
We describe the theory and implementation of two extensions to the density-matrix renormalization-group (DMRG) algorithm in quantum chemistry: (i) to work with an underlying nonorthogonal one-particle basis (using a biorthogonal formulation) and (ii) to use non-Hermitian and complex operators and complex wave functions, which occur naturally in biorthogonal formulations. Using these developments, we carry out ground-state calculations on ethene, butadiene, and hexatriene, in a polarized atomic-orbital basis. The description of correlation in these systems using a localized nonorthogonal basis is improved over molecular-orbital DMRG calculations, and comparable to or better than coupled-cluster calculations, although we encountered numerical problems associated with non-Hermiticity. We believe that the non-Hermitian DMRG algorithm may further become useful in conjunction with other non-Hermitian Hamiltonians, for example, similarity-transformed coupled-cluster Hamiltonians.
- OSTI ID:
- 20722244
- Journal Information:
- Journal of Chemical Physics, Vol. 122, Issue 20; Other Information: DOI: 10.1063/1.1899124; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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