From electronic excitation energies to spectra
Research context
research method · established · As of 2026-10-10
A computed vertical electronic excitation is not automatically a measured spectral maximum.
Key knowledge
A computed vertical electronic excitation is not automatically a measured spectral maximum. State character, basis adequacy and electronic truncation must be assessed, and nuclear/vibronic and environment contributions must be considered when comparing with experiment.
Conditions and scope
- EOM-CCSD is less reliable for substantial double-excitation character; use independently measured spectra rather than treating model agreement as proof of mechanism.
Sources · 3
References
Sources retain their recorded scope. A source link alone does not establish verification of every statement.
- Q-Chem 7.0: Excited states via EOM-EE-CCSD and EOM-CCSDTQ-Chem developersReference guide
Yuki Kobayashi, Daniel M. Neumark and Stephen R. Leone2 sources
- Attosecond XUV probing of vibronic quantum superpositions in Br2+ · accessible manuscriptYuki Kobayashi, Daniel M. Neumark and Stephen R. LeoneResearch abstract
- Attosecond XUV probing of vibronic quantum superpositions in Br2+ · Phys. Rev. A 102, 051102(R)Yuki Kobayashi, Daniel M. Neumark and Stephen R. LeoneResearch abstract
Evidence and review
Q-Chem 7.0: Excited states via EOM-EE-CCSD and EOM-CCSDT: Section 7.9.2: excitation operator and singly/doubly excited state limitations (relevant full-text sections); Attosecond XUV probing of vibronic quantum superpositions in Br2+ · accessible manuscript: Author manuscript abstract: measured coherent oscillations and modeled anharmonic/spin-orbit contributions; initial manuscript date is distinct from journal publication (author manuscript abstract); Attosecond XUV probing of vibronic quantum superpositions in Br2+ · Phys. Rev. A 102, 051102(R): Publisher abstract and metadata: prepared Br2+ attosecond transient absorption; measured Br-3d quantum beats versus quantum-mechanical attribution of decoherence to nuclear-wave-packet phase distributions on anharmonic potentials (publisher abstract and publication metadata; subscription methods and supplementary calculations not inspected)
2026-10-10 · Bounded author source inspection of from electronic excitation energies to spectra, including the stated conditions; independent branch review is recorded separately.
Entry details
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- res-chem-computed-spectrum
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- research.1
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- Postgraduate & research reference