MP2 - Maple Help

QuantumChemistry

 MP2
 compute the ground state energy of a molecule by second-order many-body perturbation theory

 Calling Sequence MP2(molecule, options)
 Parameters

 molecule - list of lists; each list has 4 elements, the string of an atom's symbol and atom's x, y, and z coordinates options - (optional) equation(s) of the form option = value where option is one of symmetry, unit,  max_memory, nuclear_gradient, return_rdm, populations, conv_tol_hf, diis_hf, diis_space_hf, diis_start_cycle_hf, direct_scf_hf, direct_scf_tol_hf, level_shift_hf, max_cycle_hf, max_memory_scf_hf, nuclear_gradient_hf, populations_hf

Description

 • Second-order many-body perturbation theory (MP2) computes the ground state of a many-electron atom or molecule with the correlation energy treated by a second-order perturbation expansion around the Hartree-Fock energy.
 • MP2 is non-variational, meaning that its energy is not necessarily an upper bound to the full CI energy in a given basis set.

Outputs

The table of following contents:

 ${t}\left[{\mathrm{e_tot}}\right]$ - float -- total electronic energy of the system ${t}\left[{\mathrm{e_corr}}\right]$ - float -- the difference between the MP2 energy and the Hartree-Fock energy ${t}\left[{\mathrm{mo_coeff}}\right]$ - Matrix -- coefficients expressing molecular orbitals (columns) in terms of atomic orbitals (rows) ${t}\left[{\mathrm{mo_occ}}\right]$ - Vector -- molecular orbital occupations ${t}\left[{\mathrm{t2}}\right]$ - Array -- two-electron transition amplitudes ${t}\left[{\mathrm{rdm1}}\right]$ - Matrix -- one-particle reduced density matrix (1-RDM) in molecular-orbital (MO) representation ${t}\left[{\mathrm{rdm2}}\right]$ - Array -- two-particle reduced density matrix (2-RDM) in molecular-orbital (MO) representation ${t}\left[{\mathrm{nuclear_gradient}}\right]$ - Matrix -- analytical nuclear gradient ${t}\left[{\mathrm{dipole}}\right]$ - Vector -- dipole moment according to its x, y and z components ${t}\left[{\mathrm{populations}}\right]$ - Matrix -- atomic-orbital populations ${t}\left[{\mathrm{charges}}\right]$ - Vector -- atomic charges from the populations

 Options
 • basis = string -- name of the basis set.  See Basis for a list of available basis sets.  Default is "sto-3g".
 • spin = nonnegint -- twice the total spin S (= 2S). Default is 0.
 • charge = nonnegint -- net charge of the molecule. Default is 0.
 • symmetry = string/boolean -- is the Schoenflies symbol of the abelian point-group symmetry which can be one of the following:  D2h, C2h, C2v, D2, Cs, Ci, C2, C1. true finds the appropriate symmetry while false (default) does not use symmetry.
 • unit = string -- "Angstrom" or "Bohr". Default is "Angstrom".
 • max_memory = posint -- allowed memory in MB. Default is 4000.
 • nuclear_gradient = boolean -- option to return the analytical nuclear gradient if available. Default is false.
 • return_rdm = string -- options to return the 1-RDM and/or 2-RDM: "none", "rdm1", "rdm1_and_rdm2". Default is "rdm1".
 • populations = string -- atomic-orbital population analysis: "Mulliken" and "Mulliken/meta-Lowdin". Default is "Mulliken".
 • Attributes for Hartree Fock:
 • conv_tol_hf = float -- converge threshold. Default is ${10}^{-10}.$
 • diis_hf = boolean -- whether to employ diis. Default is true.
 • diis_space_hf = posint -- diis's space size. By default, 8 Fock matrices and error vectors are stored.
 • diis_start_cycle_hf = posint -- the step to start diis. Default is 1.
 • direct_scf_hf = boolean -- direct SCF in which integrals are recomputed is used by default.
 • direct_scf_tol_hf = float -- direct SCF cutoff threshold. Default is ${10}^{-13}.$
 • level_shift_hf = float/int -- level shift (in au) for virtual space. Default is $0.$
 • max_cycle_hf = posint -- max number of iterations. Default is 50.
 • max_memory_scf_hf = posint -- allowed memory in MB. Default is 4000.
 • nuclear_gradient_hf = boolean -- option to return the analytical nuclear gradient. Default is false.
 • populations_hf = string -- atomic-orbital population analysis: "Mulliken" and "Mulliken/meta-Lowdin". Default is "Mulliken".

References

 1 C. Møller and M. S. Plesset, Phys. Rev. 46, 618–622 (1934). "Note on an Approximation Treatment for Many-Electron Systems"
 2 A. Szabo and N. S. Ostlund, Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory (Dover Books, New York, 1996).

Examples

 > $\mathrm{with}\left(\mathrm{QuantumChemistry}\right):$

An MP2 calculation of the  molecule

 >
 ${\mathrm{molecule}}{≔}\left[\left[{"H"}{,}{0}{,}{0}{,}{0}\right]{,}\left[{"F"}{,}{0}{,}{0}{,}{0.95000000}\right]\right]$ (1)
 >
 ${\mathrm{table}}{}\left({\mathrm{%id}}{=}{18446744735189008926}\right)$ (2)
 >