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Article: Recent advances in explicitly correlated coupled-cluster response theory for excited states and optical properties

TitleRecent advances in explicitly correlated coupled-cluster response theory for excited states and optical properties
Authors
KeywordsDipole moment
Equation of motion
Excited state
Explicitly correlated coupled-cluster
Optical property
Response theory
Issue Date2010
PublisherOldenbourg Wissenschaftsverlag GmbH.
Citation
Zeitschrift fur Physikalische Chemie, 2010, v. 224 n. 3-4, p. 383-395 How to Cite?
AbstractThe derivation of coupled-cluster response theory for explicitly correlated wavefunctions with terms linear in the interelectronic distance r12 (CC-R 12) or a function f12 thereof (CC-Fl 2) is reviewed and an implementation at the CCSD(R12) and CCSD(F12) for excitation energies and the linear, quadratic and cubic reponse functions is reported for ansätze 1 and 2. We discuss the results of first applications for vertical excitation energies, excited state equilibrium structures and vibrational frequencies, polarizabilities and first and second hyperpolarizabilities with focus on present limitations and future prospects of the approach. We show in particular that the standard choice of the geminal functions and wavefunction expansion can in certain cases lead to a bias towards the unperturbed ground state and how this can be avoided by extending the geminal space. If taken care of this, in particular CCSD(Fl2)/ansatz 2 shows for the potential energy curves of excited states and for optical properties a similar enhanced basis set convergence of the correlation contribution due to connected double excitations as for ground state energies. For diffuse excited states and hyperpolarizbilities the correlation contribution converges with CCSD(F12)/ansatz 2 often faster than orbital relaxation contributions. The convergence of the latter can be improved by allowing single excitations into a space spanned by a complementary auxiliary basis set.
Persistent Identifierhttp://hdl.handle.net/10722/231086
ISSN
2015 Impact Factor: 1.183
2015 SCImago Journal Rankings: 0.491

 

DC FieldValueLanguage
dc.contributor.authorYang, J-
dc.contributor.authorHättig, C-
dc.date.accessioned2016-09-02T06:18:51Z-
dc.date.available2016-09-02T06:18:51Z-
dc.date.issued2010-
dc.identifier.citationZeitschrift fur Physikalische Chemie, 2010, v. 224 n. 3-4, p. 383-395-
dc.identifier.issn0942-9352-
dc.identifier.urihttp://hdl.handle.net/10722/231086-
dc.description.abstractThe derivation of coupled-cluster response theory for explicitly correlated wavefunctions with terms linear in the interelectronic distance r12 (CC-R 12) or a function f12 thereof (CC-Fl 2) is reviewed and an implementation at the CCSD(R12) and CCSD(F12) for excitation energies and the linear, quadratic and cubic reponse functions is reported for ansätze 1 and 2. We discuss the results of first applications for vertical excitation energies, excited state equilibrium structures and vibrational frequencies, polarizabilities and first and second hyperpolarizabilities with focus on present limitations and future prospects of the approach. We show in particular that the standard choice of the geminal functions and wavefunction expansion can in certain cases lead to a bias towards the unperturbed ground state and how this can be avoided by extending the geminal space. If taken care of this, in particular CCSD(Fl2)/ansatz 2 shows for the potential energy curves of excited states and for optical properties a similar enhanced basis set convergence of the correlation contribution due to connected double excitations as for ground state energies. For diffuse excited states and hyperpolarizbilities the correlation contribution converges with CCSD(F12)/ansatz 2 often faster than orbital relaxation contributions. The convergence of the latter can be improved by allowing single excitations into a space spanned by a complementary auxiliary basis set.-
dc.languageeng-
dc.publisherOldenbourg Wissenschaftsverlag GmbH.-
dc.relation.ispartofZeitschrift fur Physikalische Chemie-
dc.subjectDipole moment-
dc.subjectEquation of motion-
dc.subjectExcited state-
dc.subjectExplicitly correlated coupled-cluster-
dc.subjectOptical property-
dc.subjectResponse theory-
dc.titleRecent advances in explicitly correlated coupled-cluster response theory for excited states and optical properties-
dc.typeArticle-
dc.identifier.emailYang, J: junyang4711@gmail.com-
dc.identifier.authorityYang, J=rp02186-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1524/zpch.2010.6112-
dc.identifier.scopuseid_2-s2.0-77953315131-
dc.identifier.volume224-
dc.identifier.issue3-4-
dc.identifier.spage383-
dc.identifier.epage395-

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