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Intruder state

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Multi-reference wavefunction methods are not immune. There are ways to identity them. The natural orbitals of the perturbation expansion are a useful diagnostic for detecting intruder state effects. Sometimes what appears to be an intruder state is simply a change in basis.
32:, where the energy of the perturbers is comparable in magnitude to the energy associated to the zero order wavefunction. In this case, a divergent behavior occurs, due to the nearly zero denominator in the expression of the perturbative correction. 127:
Glaesemann, Kurt R.; Govind, Niranjan; Krishnamoorthy, Sriram; Kowalski, Karol (2010). "EOMCC, MRPT, and TDDFT Studies of Charge Transfer Processes in Mixed-Valence Compounds: Application to the Spiro Molecule†".
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Choe, Yoong-Kee; Witek, Henryk A.; Finley, James P.; Hirao, Kimihiko (2001). "Identifying and removing intruder states in multireference Mo̸ller–Plesset perturbation theory".
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Camacho, Cristopher; Witek, Henryk A.; Yamamoto, Shigeyoshi (2009). "Intruder states in multireference perturbation theory: The ground state of manganese dimer".
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Gordon, Mark S.; Schmidt, Michael W.; Chaban, Galina M.; Glaesemann, Kurt R.; Stevens, Walter J.; Gonzalez, Carlos (1999).
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Glaesemann, Kurt R.; Schmidt, Michael W. (2010). "On the Ordering of Orbital Energies in High-Spin ROHF†".
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Glaesemann, Kurt R.; Gordon, Mark S.; Nakano, Haruyuki (1999).
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Index

quantum
theoretical chemistry
perturbative evaluations


"A study of FeCO+ with correlated wavefunctions"
Bibcode
1999PCCP....1..967G
doi
10.1039/a808518h
S2CID
55761535
cite journal
link
Bibcode
2010JPCA..114.8764G
doi
10.1021/jp101761d
PMID
20540550
S2CID
30757230
Bibcode
2001JChPh.114.3913C
doi
10.1063/1.1345510
CiteSeerX
10.1.1.1010.7287
doi
10.1002/jcc.21074

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