Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks
- Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
- Department of Chemistry, Boston University, Boston, Massachusetts 02215-2521 (United States)
- Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588 (United States)
- Department of Chemistry, University of California, Berkeley, California 94720 (United States)
A production-level implementation of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) for electron attachment and excitation energies augmented by a complex absorbing potential (CAP) is presented. The new method enables the treatment of metastable states within the EOM-CC formalism in a similar manner as bound states. The numeric performance of the method and the sensitivity of resonance positions and lifetimes to the CAP parameters and the choice of one-electron basis set are investigated. A protocol for studying molecular shape resonances based on the use of standard basis sets and a universal criterion for choosing the CAP parameters are presented. Our results for a variety of π{sup *} shape resonances of small to medium-size molecules demonstrate that CAP-augmented EOM-CCSD is competitive relative to other theoretical approaches for the treatment of resonances and is often able to reproduce experimental results.
- OSTI ID:
- 22308766
- Journal Information:
- Journal of Chemical Physics, Vol. 141, Issue 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: Theory, implementation, and examples
Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations