Efficient automated implementation of higher-order many-body methods in quantum chemistry

To follow up on the unexpectedly-good performance of coupled-cluster models with approx- imate inclusion of 3-body clusters [J. Chem. Phys. 151, 064102 (2019)] we performed a more complete assessment of the 3CC method [J. Chem. Phys. 125, 204105 (2006)] for accurate computational thermochemistry in the standard HEAT framework. New spin- integrated implementation of the 3CC method applicable to closed- and open-shell systems utilizes a new automated toolchain for derivation, optimization, and evaluation of operator algebra in many-body electronic structure. We found that with a double-zeta basis set the 3CC correlation energies and their atomization energy contributions are almost always more accurate (with respect to the CCSDTQ reference) than the CCSDT model as well as the standard CCSD(T) model. The mean errors in { 3CC, CCSDT, and CCSD(T) } electronic (per valence electron) and atomization energies were {23, 69, 125} μEh/e and {0.39, 1.92, 2.57} kJ/mol, respectively. The significant and systematic reduction of the error by the 3CC method and its lower cost than CCSDT suggests it as a viable candidate for post-CCSD(T) thermochemistry application.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2023

Author dc:creator

• Teke, Nakul Kushabhau

Chair dc:contributor.committeechair

• Valeyev, Eduard Faritovich

Committee members dc:contributor.committeemember

• Troya, Diego
• Crawford, Daniel
• Mayhall, Nicholas

• Explicitly correlated many-body methods
• Green's function
• coupled cluster
• spin tracing
• spin adaptation

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Dc Identifier Other

vt_gsexam:36211

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/113605