Systematic truncation of the virtual space in multiconfigurational perturbation theory
(2009) In Journal of Chemical Physics 131(3).- Abstract
- A method is suggested which allows truncation of the virtual space in Cholesky decomposition-based multiconfigurational perturbation theory (CD-CASPT2) calculations with systematic improvability of the results. The method is based on a modified version of the frozen natural orbital (FNO) approach used in coupled cluster theory. The idea is to exploit the near-linear dependence among the eigenvectors of the virtual-virtual block of the second-order Moller-Plesset density matrix. It is shown that FNO-CASPT2 recovers more than 95% of the full CD-CASPT2 correlation energy while requiring only a fraction of the total virtual space, especially when large atomic orbital basis sets are in use. Tests on various properties commonly investigated with... (More)
- A method is suggested which allows truncation of the virtual space in Cholesky decomposition-based multiconfigurational perturbation theory (CD-CASPT2) calculations with systematic improvability of the results. The method is based on a modified version of the frozen natural orbital (FNO) approach used in coupled cluster theory. The idea is to exploit the near-linear dependence among the eigenvectors of the virtual-virtual block of the second-order Moller-Plesset density matrix. It is shown that FNO-CASPT2 recovers more than 95% of the full CD-CASPT2 correlation energy while requiring only a fraction of the total virtual space, especially when large atomic orbital basis sets are in use. Tests on various properties commonly investigated with CASPT2 demonstrate the reliability of the approach and the associated reduction in computational cost and storage demand of the calculations. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1461539
- author
- Aquilante, Francesco ; Todorova, Tanya Kumanova ; Gagliardi, Laura ; Pedersen, Thomas LU and Roos, Björn LU
- organization
- publishing date
- 2009
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- decomposition, matrix, coupled cluster calculations, eigenvalues and eigenfunctions, physics computing, perturbation theory
- in
- Journal of Chemical Physics
- volume
- 131
- issue
- 3
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000268206800019
- scopus:67651213466
- pmid:19624187
- ISSN
- 0021-9606
- DOI
- 10.1063/1.3157463
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 11e95a58-bc95-4a05-b84d-90e8ce9fc374 (old id 1461539)
- date added to LUP
- 2016-04-01 11:38:45
- date last changed
- 2023-01-02 21:15:52
@article{11e95a58-bc95-4a05-b84d-90e8ce9fc374, abstract = {{A method is suggested which allows truncation of the virtual space in Cholesky decomposition-based multiconfigurational perturbation theory (CD-CASPT2) calculations with systematic improvability of the results. The method is based on a modified version of the frozen natural orbital (FNO) approach used in coupled cluster theory. The idea is to exploit the near-linear dependence among the eigenvectors of the virtual-virtual block of the second-order Moller-Plesset density matrix. It is shown that FNO-CASPT2 recovers more than 95% of the full CD-CASPT2 correlation energy while requiring only a fraction of the total virtual space, especially when large atomic orbital basis sets are in use. Tests on various properties commonly investigated with CASPT2 demonstrate the reliability of the approach and the associated reduction in computational cost and storage demand of the calculations.}}, author = {{Aquilante, Francesco and Todorova, Tanya Kumanova and Gagliardi, Laura and Pedersen, Thomas and Roos, Björn}}, issn = {{0021-9606}}, keywords = {{decomposition; matrix; coupled cluster calculations; eigenvalues and eigenfunctions; physics computing; perturbation theory}}, language = {{eng}}, number = {{3}}, publisher = {{American Institute of Physics (AIP)}}, series = {{Journal of Chemical Physics}}, title = {{Systematic truncation of the virtual space in multiconfigurational perturbation theory}}, url = {{http://dx.doi.org/10.1063/1.3157463}}, doi = {{10.1063/1.3157463}}, volume = {{131}}, year = {{2009}}, }