6.6 Auxiliary Basis (Resolution of the Identity) MP2 Methods

6.6.1 RI-MP2 Energies and Gradients.

Following common convention, the MP2 energy evaluated approximately using an auxiliary basis is referred to as “resolution of the identity” MP2, or RI-MP2 for short. RI-MP2 energy and gradient calculations are enabled simply by specifying the AUX_BASIS keyword discussed above. As discussed above, RI-MP2 energies260 and gradients963, 229 are significantly faster than the best conventional MP2 energies and gradients, and cause negligible loss of accuracy, when an appropriate standardized auxiliary basis set is employed. Therefore they are recommended for jobs where turnaround time is an issue. Disk requirements are very modest; one merely needs to hold various 3-index arrays. Memory requirements grow more slowly than our conventional MP2 algorithms—only quadratically with molecular size. The minimum memory requirement is approximately 3X2, where X is the number of auxiliary basis functions, for both energy and analytical gradient evaluations, with some additional memory being necessary for integral evaluation and other small arrays.

In fact, for molecules that are not too large (perhaps no more than 20 or 30 heavy atoms) the RI-MP2 treatment of electron correlation is so efficient that the computation is dominated by the initial Hartree-Fock calculation. This is despite the fact that as a function of molecule size, the cost of the RI-MP2 treatment still scales more steeply with molecule size (it is just that the pre-factor is so much smaller with the RI approach). Its scaling remains 5th order with the size of the molecule, which only dominates the initial SCF calculation for larger molecules. Thus, for RI-MP2 energy evaluation on moderate size molecules (particularly in large basis sets), it is desirable to use the dual basis HF method to further improve execution times (see Section 4.7).

For the size of required memory, the followings need to be considered.

MEM_STATIC
       Sets the memory for AO-integral evaluations and their transformations in Q-Chem 4.1 or older versions.
TYPE:
       INTEGER
DEFAULT:
       64 corresponding to 64 MB.
OPTIONS:
       n User-defined number of megabytes.
RECOMMENDATION:
       For RI-MP2 calculations using Q-Chem 4.1 or older versions, 150(ON+V) of MEM_STATIC is required. Because a number of matrices with N2 size also need to be stored, 32–160 MB of additional MEM_STATIC is needed.

MEM_TOTAL
       Sets the total memory available to Q-Chem, in megabytes.
TYPE:
       INTEGER
DEFAULT:
       2000 2 GB
OPTIONS:
       n User-defined number of megabytes.
RECOMMENDATION:
       Use the default, or set to the physical memory of your machine. The minimum requirement is 3X2.

Example 6.3  Q-Chem input for an RI-MP2 geometry optimization.

$molecule
   0 1
   O
   H  1  0.9
   F  1  1.4  2  100.
$end

$rem
   JOBTYPE       opt
   METHOD        rimp2
   BASIS         cc-pvtz
   AUX_BASIS     rimp2-cc-pvtz
   SYMMETRY      false
$end