In quantum and theoretical chemistry, an intruder state is a particular situation arising in perturbative evaluations, 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.
Multi-reference wavefunction methods are not immune. [1] [2] There are ways to identity them. [3] [4] The natural orbitals of the perturbation expansion are a useful diagnostic for detecting intruder state effects. [5] Sometimes what appears to be an intruder state is simply a change in basis. [1] [6]
References
- ^ a b Glaesemann, Kurt R.; Gordon, Mark S.; Nakano, Haruyuki (1999). "A study of FeCO+ with correlated wavefunctions" (PDF). Physical Chemistry Chemical Physics. 1 (6): 967–975. Bibcode: 1999PCCP....1..967G. doi: 10.1039/a808518h. S2CID 55761535.
- ^ 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†". The Journal of Physical Chemistry A. 114 (33): 8764–8771. Bibcode: 2010JPCA..114.8764G. doi: 10.1021/jp101761d. PMID 20540550. S2CID 30757230.
- ^ Choe, Yoong-Kee; Witek, Henryk A.; Finley, James P.; Hirao, Kimihiko (2001). "Identifying and removing intruder states in multireference Mo̸ller–Plesset perturbation theory". The Journal of Chemical Physics. 114 (9): 3913–3918. Bibcode: 2001JChPh.114.3913C. doi: 10.1063/1.1345510.
- ^ Camacho, Cristopher; Witek, Henryk A.; Yamamoto, Shigeyoshi (2009). "Intruder states in multireference perturbation theory: The ground state of manganese dimer". Journal of Computational Chemistry. 30 (3): 468–478. CiteSeerX 10.1.1.1010.7287. doi: 10.1002/jcc.21074. hdl: 11536/7682. PMID 18680217. S2CID 5649816.
- ^ Gordon, Mark S.; Schmidt, Michael W.; Chaban, Galina M.; Glaesemann, Kurt R.; Stevens, Walter J.; Gonzalez, Carlos (1999). "A natural orbital diagnostic for multiconfigurational character in correlated wave functions". The Journal of Chemical Physics. 110 (9): 4199–4207. Bibcode: 1999JChPh.110.4199G. doi: 10.1063/1.478301. hdl: 20.500.12876/14794. S2CID 480255.
- ^ Glaesemann, Kurt R.; Schmidt, Michael W. (2010). "On the Ordering of Orbital Energies in High-Spin ROHF†". The Journal of Physical Chemistry A. 114 (33): 8772–8777. Bibcode: 2010JPCA..114.8772G. doi: 10.1021/jp101758y. OSTI 988621. PMID 20443582. S2CID 12313638.
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In quantum and theoretical chemistry, an intruder state is a particular situation arising in perturbative evaluations, 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.
Multi-reference wavefunction methods are not immune. [1] [2] There are ways to identity them. [3] [4] The natural orbitals of the perturbation expansion are a useful diagnostic for detecting intruder state effects. [5] Sometimes what appears to be an intruder state is simply a change in basis. [1] [6]
References
- ^ a b Glaesemann, Kurt R.; Gordon, Mark S.; Nakano, Haruyuki (1999). "A study of FeCO+ with correlated wavefunctions" (PDF). Physical Chemistry Chemical Physics. 1 (6): 967–975. Bibcode: 1999PCCP....1..967G. doi: 10.1039/a808518h. S2CID 55761535.
- ^ 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†". The Journal of Physical Chemistry A. 114 (33): 8764–8771. Bibcode: 2010JPCA..114.8764G. doi: 10.1021/jp101761d. PMID 20540550. S2CID 30757230.
- ^ Choe, Yoong-Kee; Witek, Henryk A.; Finley, James P.; Hirao, Kimihiko (2001). "Identifying and removing intruder states in multireference Mo̸ller–Plesset perturbation theory". The Journal of Chemical Physics. 114 (9): 3913–3918. Bibcode: 2001JChPh.114.3913C. doi: 10.1063/1.1345510.
- ^ Camacho, Cristopher; Witek, Henryk A.; Yamamoto, Shigeyoshi (2009). "Intruder states in multireference perturbation theory: The ground state of manganese dimer". Journal of Computational Chemistry. 30 (3): 468–478. CiteSeerX 10.1.1.1010.7287. doi: 10.1002/jcc.21074. hdl: 11536/7682. PMID 18680217. S2CID 5649816.
- ^ Gordon, Mark S.; Schmidt, Michael W.; Chaban, Galina M.; Glaesemann, Kurt R.; Stevens, Walter J.; Gonzalez, Carlos (1999). "A natural orbital diagnostic for multiconfigurational character in correlated wave functions". The Journal of Chemical Physics. 110 (9): 4199–4207. Bibcode: 1999JChPh.110.4199G. doi: 10.1063/1.478301. hdl: 20.500.12876/14794. S2CID 480255.
- ^ Glaesemann, Kurt R.; Schmidt, Michael W. (2010). "On the Ordering of Orbital Energies in High-Spin ROHF†". The Journal of Physical Chemistry A. 114 (33): 8772–8777. Bibcode: 2010JPCA..114.8772G. doi: 10.1021/jp101758y. OSTI 988621. PMID 20443582. S2CID 12313638.
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