A quadratically convergent multiconfiguration–self-consistent field method with simultaneous optimization of orbitals and CI coefficients

Journal of Chemical Physics - Tập 73 Số 5 - Trang 2342-2356 - 1980
Hans‐Joachim Werner1, Wilfried Meyer2
1Institut für Physikalische und theoretische Chemie der Universität Frankfurt/M, West Germany
2Institut für Physikalische Chemie der Universität Kaiserslautern, West Germany

Tóm tắt

A quadratically convergent MC–SCF procedure is described which is based on the direct minimization of the energy. In comparison to the Newton–Raphson technique, which has previously been applied by several authors for orbital optimization, the convergence radius is much improved by taking into account in the energy expansion those parts of third and higher order terms which account exactly for the orthonormality constraints imposed on the orbitals. The nonlinear equations which define the improved orbitals are solved iteratively by a simple adaption of the Gauss–Seidel method. The coefficients of the configuration expansion can be optimized simultaneously with the orbitals, a necessary requirement for over-all quadratic convergence. The removal of redundant variables as well as useful approximations for the optimization of core orbitals are discussed. The convergence of the method is demonstrated to be much superior to classical Fock operator techniques and MC–SCF methods which are based on the generalized Brillouin theorem. The formalism is carried down to matrix operations and shows a simple structure.

Từ khóa


Tài liệu tham khảo

1960, Rev. Mod. Phys., 32, 179, 10.1103/RevModPhys.32.179

1960, Phys. Rev., 120, 866, 10.1103/PhysRev.120.866

1961, Phys. Rev., 122, 131, 10.1103/PhysRev.122.131

1963, J. Chem. Phys., 38, 2552, 10.1063/1.1733540

1964, J. Chem. Phys., 40, 3212, 10.1063/1.1724987

1964, J. Chem. Phys., 40, 3203, 10.1063/1.1724985

1964, J. Chem. Phys., 40, 3207, 10.1063/1.1724986

1966, J. Chem. Phys., 44, 87, 10.1063/1.1726508

1967, J. Chem. Phys., 47, 2934, 10.1063/1.1712318

1967, J. Chem. Phys., 46, 1568, 10.1063/1.1840904

1967, Theoret. Chim. Acta (Berl.), 7, 133, 10.1007/BF01151915

1967, Suppl. Prog. Theor. Phys., 40, 37, 10.1143/PTPS.40.37

1969, Prog. Theor. Phys., 41, 307, 10.1143/PTP.41.307

1969, J. Chem. Phys., 51, 3971, 10.1063/1.1672617

1969, Chem. Phys. Lett., 4, 231, 10.1016/0009-2614(69)80170-3

1972, J. Chem. Phys., 56, 1769, 10.1063/1.1677438

1973, J. Chem. Phys., 58, 5104, 10.1063/1.1679100

1973, J. Chem. Phys., 59, 1457, 10.1063/1.1680203

1973, J. Chem. Phys., 60, 3215

1973, Mol. Phys., 26, 595, 10.1080/00268977300101921

1974, Int. J. Quant. Chem., 8, 373, 10.1002/qua.560080306

1975, Chem. Phys. Lett., 30, 43, 10.1016/0009-2614(75)85494-7

1976, Theoret. Chim. Acta (Berl.), 42, 193, 10.1007/BF00547073

1976, Chem. Phys. Lett., 37, 597, 10.1016/0009-2614(76)85047-6

1973, J. Chem. Phys., 59, 6424, 10.1063/1.1680022

1979, J. Chem. Phys., 70, 3188, 10.1063/1.437906

1971, Chem. Phys. Lett., 12, 44, 10.1016/0009-2614(71)80612-7

1975, Int. J. Quant. Chem. Symp., 9, 147

1976, Int. J. Quant. Chem., 10, 123, 10.1002/qua.560100110

1977, Theoret. Chim. Acta (Berl.), 44, 97, 10.1007/BF00549094

1977, Theoret. Chim. Acta (Berl.), 44, 45, 10.1007/BF00548028

1979, Int. J. Quant. Chem., 16, 1068

1968, Int. J. Quant. Chem., 2, 307, 10.1002/qua.560020210

1969, Chem. Phys. Lett., 4, 17, 10.1016/0009-2614(69)85022-0

1970, Int. J. Quant. Chem., 4, 297, 10.1002/qua.560040307

1973, Chem. Phys. Lett., 18, 59, 10.1016/0009-2614(73)80338-0

1975, Int. J. Quant. Chem., 9, 1009, 10.1002/qua.560090608

1976, Int. J. Quant. Chem., 10, 941, 10.1002/qua.560100603

1975, Theor. Chim. Acta, 40, 245, 10.1007/BF00548459

1976, Theor. Chim. Acta, 41, 311, 10.1007/BF01177999

1977, Theor. Chim. Acta, 45, 317, 10.1007/BF00554540

1974, Theor. Chim. Acta, 33, 201, 10.1007/BF00551255

1975, Theor. Chim. Acta, 39, 93, 10.1007/BF00547789

1975, Mol. Phys., 30, 1203, 10.1080/00268977500102741

1976, Phys. Rev. A, 13, 1682, 10.1103/PhysRevA.13.1682

1976, Chem. Phys. Lett., 41, 283, 10.1016/0009-2614(76)80811-1

1978, J. Chem. Phys., 69, 3833, 10.1063/1.437049

1979, J. Chem. Phys., 71, 755, 10.1063/1.438363

1979, J. Chem. Phys., 70, 1101, 10.1063/1.437609

Thông tin
Thông tin xuất bản

Journal of Chemical Physics

Tập 73 Số 5

2342-2356

Thông tin tác giả