A theoretical study of the lowest-energy singlet and triplet electronic states p -iminophosphaalkyne and nitrilimine
Identifieur interne : 001C40 ( Main/Exploration ); précédent : 001C39; suivant : 001C41A theoretical study of the lowest-energy singlet and triplet electronic states p -iminophosphaalkyne and nitrilimine
Auteurs : Kathleen Kuhler [États-Unis] ; Roger T. Palmer [États-Unis] ; Brian L. Wittkamp [États-Unis] ; Mark R. Hoffmann [États-Unis]Source :
- Journal of Molecular Structure: THEOCHEM [ 0166-1280 ] ; 1996.
English descriptors
- Teeft :
- Active orbitals, Basis sets, Bond angle, Bond angles, Bond length, Bond lengths, Bond stretch frequency, Carbon atom, Casscf, Casscf equilibrium geometry, Chem, Core orbitals, Differential basis, Dihedral, Dihedral angles, Double bond, Double bonds, Double excitations, Dynamic electron correlation, Electron correlation, Electronic states, Electronic structure, Energy separation, Equilibrium geometries, Equilibrium geometry, Excitation, Fundamental vibrational frequencies, Further details, Geometry, Geometry optimization, Geometry optimizations, H2pch, H2pn, Hcnnh, Hcpnh, Heavy atoms, Hehre, Kcal, Kcal mall, Kuhler, Mcscf, Mcscf wavefunctions, Model space, Molecular structure, Nitrilimine, Optimization, Optimized, Optimized geometries, Optimized geometry, Orbitals, Polarization functions, Pople, Rohf, Single bond, Singlet, Singlet h2pch, Singlet hcnnh, Singlet hcpnh, Singlet state, Stretch frequencies, Stretch frequency, Theochem, Triple bond, Triplet, Triplet hcnnh, Triplet hcpnh, Triplet state, Triplet states, Valence, Vibrational, Vibrational data, Vibrational frequencies, Wavefunctions.
Abstract
Abstract: The equilibrium geometries and fundamental vibrational frequencies of the two energetically lowest-lying electronic states of p-iminophosphaalkyne (HCPNH) and nitrilimine (HCNNH) were determined using a split-valence basis set with polarization functions on the heavy atoms. The most extensively correlated functions used in the geometry optimizations were of the Complete Active Space Self-Consistent Field (CASSCF) variety and included eight electrons distributed among seven active orbitals for HCPNH and six active orbitals for HCNNH. The effects on predicted geometry of the size of the CASSCF active space were investigated for HCPNH and are reported. Multi-Reference Configuration Interaction with Single and Double excitations calculations have been performed at the equilibrium geometries using larger basis sets to determine more accurately the relative energetics of the electronic states. It was found that nitrilimine has the expected singlet ground state, with the triplet lying 38.5 kcal mol−1 higher in energy; however, p-iminophosphaalkyne has a triplet ground state, lying 9.7 kcal mol−1 below the singlet.
Url:
DOI: 10.1016/0166-1280(95)04356-X
Affiliations:
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Palmer</name><affiliation wicri:level="2"><country xml:lang="fr">États-Unis</country><wicri:regionArea>University of North Dakota, Chemistry Department, Grand Forks, ND 58202-9024</wicri:regionArea><placeName><region type="state">Dakota du Nord</region></placeName></affiliation></author><author><name sortKey="Wittkamp, Brian L" sort="Wittkamp, Brian L" uniqKey="Wittkamp B" first="Brian L." last="Wittkamp">Brian L. Wittkamp</name><affiliation wicri:level="2"><country xml:lang="fr">États-Unis</country><wicri:regionArea>University of North Dakota, Chemistry Department, Grand Forks, ND 58202-9024</wicri:regionArea><placeName><region type="state">Dakota du Nord</region></placeName></affiliation></author><author><name sortKey="Hoffmann, Mark R" sort="Hoffmann, Mark R" uniqKey="Hoffmann M" first="Mark R." last="Hoffmann">Mark R. Hoffmann</name><affiliation wicri:level="2"><country xml:lang="fr">États-Unis</country><wicri:regionArea>University of North Dakota, Chemistry Department, Grand Forks, ND 58202-9024</wicri:regionArea><placeName><region type="state">Dakota du Nord</region></placeName></affiliation></author></analytic><monogr></monogr><series><title level="j">Journal of Molecular Structure: THEOCHEM</title><title level="j" type="abbrev">THEOCH</title><idno type="ISSN">0166-1280</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1996">1996</date><biblScope unit="volume">360</biblScope><biblScope unit="issue">1–3</biblScope><biblScope unit="page" from="41">41</biblScope><biblScope unit="page" to="54">54</biblScope></imprint><idno type="ISSN">0166-1280</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0166-1280</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="Teeft" xml:lang="en"><term>Active orbitals</term><term>Basis sets</term><term>Bond angle</term><term>Bond angles</term><term>Bond length</term><term>Bond lengths</term><term>Bond stretch frequency</term><term>Carbon atom</term><term>Casscf</term><term>Casscf equilibrium geometry</term><term>Chem</term><term>Core orbitals</term><term>Differential basis</term><term>Dihedral</term><term>Dihedral angles</term><term>Double bond</term><term>Double bonds</term><term>Double excitations</term><term>Dynamic electron correlation</term><term>Electron correlation</term><term>Electronic states</term><term>Electronic structure</term><term>Energy separation</term><term>Equilibrium geometries</term><term>Equilibrium geometry</term><term>Excitation</term><term>Fundamental vibrational frequencies</term><term>Further details</term><term>Geometry</term><term>Geometry optimization</term><term>Geometry optimizations</term><term>H2pch</term><term>H2pn</term><term>Hcnnh</term><term>Hcpnh</term><term>Heavy atoms</term><term>Hehre</term><term>Kcal</term><term>Kcal mall</term><term>Kuhler</term><term>Mcscf</term><term>Mcscf wavefunctions</term><term>Model space</term><term>Molecular structure</term><term>Nitrilimine</term><term>Optimization</term><term>Optimized</term><term>Optimized geometries</term><term>Optimized geometry</term><term>Orbitals</term><term>Polarization functions</term><term>Pople</term><term>Rohf</term><term>Single bond</term><term>Singlet</term><term>Singlet h2pch</term><term>Singlet hcnnh</term><term>Singlet hcpnh</term><term>Singlet state</term><term>Stretch frequencies</term><term>Stretch frequency</term><term>Theochem</term><term>Triple bond</term><term>Triplet</term><term>Triplet hcnnh</term><term>Triplet hcpnh</term><term>Triplet state</term><term>Triplet states</term><term>Valence</term><term>Vibrational</term><term>Vibrational data</term><term>Vibrational frequencies</term><term>Wavefunctions</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: The equilibrium geometries and fundamental vibrational frequencies of the two energetically lowest-lying electronic states of p-iminophosphaalkyne (HCPNH) and nitrilimine (HCNNH) were determined using a split-valence basis set with polarization functions on the heavy atoms. The most extensively correlated functions used in the geometry optimizations were of the Complete Active Space Self-Consistent Field (CASSCF) variety and included eight electrons distributed among seven active orbitals for HCPNH and six active orbitals for HCNNH. The effects on predicted geometry of the size of the CASSCF active space were investigated for HCPNH and are reported. Multi-Reference Configuration Interaction with Single and Double excitations calculations have been performed at the equilibrium geometries using larger basis sets to determine more accurately the relative energetics of the electronic states. It was found that nitrilimine has the expected singlet ground state, with the triplet lying 38.5 kcal mol−1 higher in energy; however, p-iminophosphaalkyne has a triplet ground state, lying 9.7 kcal mol−1 below the singlet.</div></front></TEI><affiliations><list><country><li>États-Unis</li></country><region><li>Dakota du Nord</li></region></list><tree><country name="États-Unis"><region name="Dakota du Nord"><name sortKey="Kuhler, Kathleen" sort="Kuhler, Kathleen" uniqKey="Kuhler K" first="Kathleen" last="Kuhler">Kathleen Kuhler</name></region><name sortKey="Hoffmann, Mark R" sort="Hoffmann, Mark R" uniqKey="Hoffmann M" first="Mark R." last="Hoffmann">Mark R. Hoffmann</name><name sortKey="Palmer, Roger T" sort="Palmer, Roger T" uniqKey="Palmer R" first="Roger T." last="Palmer">Roger T. Palmer</name><name sortKey="Wittkamp, Brian L" sort="Wittkamp, Brian L" uniqKey="Wittkamp B" first="Brian L." last="Wittkamp">Brian L. Wittkamp</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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