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Statements

Subject Item
n2:RIV%2F61388963%3A_____%2F13%3A00392510%21RIV14-GA0-61388963
rdf:type
skos:Concept n15:Vysledek
dcterms:description
The interaction between the Pt atom and the benzene (Bz) molecule was investigated theoretically, using a symmetric Pt Bz half-sandwich complex. Various levels of wave function theory (HF, MP2, CCSD(T), CASPT2, multistate (MS) MS-CASPT2) together with several functionals (PBE, PBE+D3, PBE+vdW, PBE/EE+vdW) of the density functional theory (DFT) were complemented by quantum Monte Carlo (QMC) calculations. Spin-orbit coupling (SOC) effects were also taken into account at the CASPT2 and DFT levels of theory. The inclusion of dynamic correlation energy was found to be essential to maintaining the stability of the complex. The dative type of bonding was identified to be responsible for the Pt-Bz binding in the ground state. Single-reference CCSD(T) and MP2 as well as multireference CASPT2 and MS-CASPT2 methods reveal that the interaction curve has a single energy minimum (corresponding to the S-1(0) state) and a shoulder (arising from the crossing between the S-1(0) and D-3(3) states) at longer distances. The inclusion of SOC at the CASPT2 level leads to the appearance of another well-separated minimum, which corresponds to the triplet state F-3(4). The PBE/EE+vdW functional, which includes a fraction of exact-exchange (EE) and nonlocal electron correlation, shows the best qualitative agreement with respect to the CCSD(T) data among all DFT functionals used. Large-scale QMC calculations, based on DFT wave functions constructed using TPSSh and M11 functionals, were confronted with the CCSD(T) results. The QMC-TPSSh protocol favorably agrees with the CCSD(T) data, suggesting its possible use in other Pt-containing organometallic systems. All of the methods used (except for HF) show that the Pt-benzene binding leads to the quenching of the Pt high-spin triplet ground state, and the low-spin closed-shell singlet state is found to be preferred in the ground-state of the complex. The interaction between the Pt atom and the benzene (Bz) molecule was investigated theoretically, using a symmetric Pt Bz half-sandwich complex. Various levels of wave function theory (HF, MP2, CCSD(T), CASPT2, multistate (MS) MS-CASPT2) together with several functionals (PBE, PBE+D3, PBE+vdW, PBE/EE+vdW) of the density functional theory (DFT) were complemented by quantum Monte Carlo (QMC) calculations. Spin-orbit coupling (SOC) effects were also taken into account at the CASPT2 and DFT levels of theory. The inclusion of dynamic correlation energy was found to be essential to maintaining the stability of the complex. The dative type of bonding was identified to be responsible for the Pt-Bz binding in the ground state. Single-reference CCSD(T) and MP2 as well as multireference CASPT2 and MS-CASPT2 methods reveal that the interaction curve has a single energy minimum (corresponding to the S-1(0) state) and a shoulder (arising from the crossing between the S-1(0) and D-3(3) states) at longer distances. The inclusion of SOC at the CASPT2 level leads to the appearance of another well-separated minimum, which corresponds to the triplet state F-3(4). The PBE/EE+vdW functional, which includes a fraction of exact-exchange (EE) and nonlocal electron correlation, shows the best qualitative agreement with respect to the CCSD(T) data among all DFT functionals used. Large-scale QMC calculations, based on DFT wave functions constructed using TPSSh and M11 functionals, were confronted with the CCSD(T) results. The QMC-TPSSh protocol favorably agrees with the CCSD(T) data, suggesting its possible use in other Pt-containing organometallic systems. All of the methods used (except for HF) show that the Pt-benzene binding leads to the quenching of the Pt high-spin triplet ground state, and the low-spin closed-shell singlet state is found to be preferred in the ground-state of the complex.
dcterms:title
Spin-Crossing in an Organometallic Pt-Benzene Complex Spin-Crossing in an Organometallic Pt-Benzene Complex
skos:prefLabel
Spin-Crossing in an Organometallic Pt-Benzene Complex Spin-Crossing in an Organometallic Pt-Benzene Complex
skos:notation
RIV/61388963:_____/13:00392510!RIV14-GA0-61388963
n15:predkladatel
n16:ico%3A61388963
n3:aktivita
n14:I n14:P
n3:aktivity
I, P(ED2.1.00/03.0058), P(EE2.3.20.0017), P(EE2.3.30.0004), P(GAP208/10/1742), P(GBP208/12/G016)
n3:cisloPeriodika
3
n3:dodaniDat
n9:2014
n3:domaciTvurceVysledku
n8:2932016 n8:4792335
n3:druhVysledku
n19:J
n3:duvernostUdaju
n12:S
n3:entitaPredkladatele
n11:predkladatel
n3:idSjednocenehoVysledku
107062
n3:idVysledku
RIV/61388963:_____/13:00392510
n3:jazykVysledku
n18:eng
n3:klicovaSlova
quantum Monte Carlo; 2nd-order perturbation-theory; density-functional theory; augmented-wave method
n3:klicoveSlovo
n7:density-functional%20theory n7:augmented-wave%20method n7:quantum%20Monte%20Carlo n7:2nd-order%20perturbation-theory
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[DC2D8E37590F]
n3:nazevZdroje
Journal of Chemical Theory and Computation
n3:obor
n17:CF
n3:pocetDomacichTvurcuVysledku
2
n3:pocetTvurcuVysledku
5
n3:projekt
n5:GAP208%2F10%2F1742 n5:GBP208%2F12%2FG016 n5:ED2.1.00%2F03.0058 n5:EE2.3.30.0004 n5:EE2.3.20.0017
n3:rokUplatneniVysledku
n9:2013
n3:svazekPeriodika
9
n3:tvurceVysledku
Otyepka, M. Granatier, Jaroslav Hobza, Pavel Dubecký, M. Lazar, P.
n3:wos
000316168700018
s:issn
1549-9618
s:numberOfPages
8
n13:doi
10.1021/ct400016c