Treating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach
Auer, Alexander A.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2017-06-27
Print Publication Date2017-07-11
Permanent link to this recordhttp://hdl.handle.net/10754/625068
MetadataShow full item record
AbstractThe validity of the main approximations used in canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) in standard chemical applications is discussed. In particular, we investigate the dependence of the results on the number of electrons included in the correlation treatment in frozen-core (FC) calculations and on the main threshold governing the accuracy of DLPNO all-electron (AE) calculations. Initially, scalar relativistic orbital energies for the ground state of the atoms from Li to Rn in the periodic table are calculated. An energy criterion is applied for determining the orbitals that can be excluded from the correlation treatment in FC coupled cluster calculations without significant loss of accuracy. The heterolytic dissociation energy (HDE) of a series of metal compounds (LiF, NaF, AlF3, CaF2, CuF, GaF3, YF3, AgF, InF3, HfF4 and AuF) is calculated at the canonical CCSD(T) level, and the dependence of the results on the number of correlated electrons is investigated. Although for many of the studied reactions sub-valence correlation effects contribute significantly to the HDE, the use of an energy criterion permits a conservative definition of the size of the core, allowing FC calculations to be performed in a black-box fashion while retaining chemical accuracy. A comparison of the CCSD and the DLPNO-CCSD methods in describing the core-core, core-valence and valence-valence components of the correlation energy is given. It is found that more conservative thresholds must be used for electron pairs containing at least one core electron in order to achieve high accuracy in AE DLPNO-CCSD calculations relative to FC calculations. With the new settings, the DLPNO-CCSD method reproduces canonical CCSD results in both AE and FC calculations with the same accuracy.
CitationBistoni G, Riplinger C, Minenkov Y, Cavallo L, Auer AA, et al. (2017) Treating sub-valence correlation effects in domain based pair natural orbital coupled cluster calculations: an out-of-the-box approach. Journal of Chemical Theory and Computation. Available: http://dx.doi.org/10.1021/acs.jctc.7b00352.
SponsorsGiovanni Bistoni, Alexander A. Auer and Frank Neese gratefully acknowledge the Priority Program ’’Control of London Dispersion Interactions in Molecular Chemistry’’ (SPP 1807) of the DFG for financial support. Yury Minenkov and Luigi Cavallo gratefully acknowledge the financial support from King Abdullah University of Science and Technology (KAUST).
PublisherAmerican Chemical Society (ACS)