Multiconfiguration self-consistent-field theory based upon the fragment molecular orbital method

Abstract

The fragment molecular orbital (FMO) method was combined with the multiconfiguration self-consistent-field (MCSCF) theory. One- and two-layer approaches were developed, the former involving all dimer MCSCF calculations and the latter limiting MCSCF calculations to a small part of the system. The accuracy of the two methods was tested using the six electrons in six orbitals complete active space type of MCSCF and singlet spin state for phenol+(H2O)n, n=16,32,64 (6-31G* and 6-311G* basis sets); α helices and β strands of phenylalanine-(alanine)n, n=4,8,16 (6-31G*). Both double-ζ and triple-ζ quality basis sets with polarization were found to have very similar accuracy. The error in the correlation energy was at most 0.000 88 a.u., the error in the gradient of the correlation energy was at most 6.×10−5 a.u./bohr and the error in the correlation correction to the dipole moment was at most 0.018 D. In addition, vertical singlet-triplet electron excitation energies were computed for phenol+(H2O)n, (n=16,32,64), 6-31G*, and the errors were found to be at most 0.02 eV. Approximately linear scaling was observed for the FMO-based MCSCF methods. As an example, an FMO-based MCSCF calculation with 1262 basis functions took 98 min on one 3.0 GHz Pentium4 node with 1 Gbyte RAM.