All-Electron Ab Initio Investigation of the Electronic States of the PdC Molecule

DAPD Set of Pd-Containing Diatomic Molecules: Accurate Molecular Properties and the Great Lengths to Obtain Them

“…The spin states for the groups 3, 5, 6, and 7 molecules are consistent with a single bond with the Pd atom. However, the singlet ground state for PdC and PdSi suggests a double bond, which is consistent with the proposition of ref . We have further obtained the triplet energy for PdC at the CCSD­(T,CV)/aug-cc-pWCVQZ level and find that it is indeed higher in energy than the corresponding singlet.…”

“…The bond energies and the contributions from the various components are given in Table . For comparison, the table also contains available literature values for the bond energies, specifically for PdH, PdB, PdC, PdO, PdF, PdAl, PdSi, and Pd 2 . Among these, the ones for PdB, PdO, PdAl, PdSi, and Pd 2 are from the experiment, while the others are from computational studies with MRCI (for PdH, and PdC) or CISD (PdF).…”

DAPD Set of Pd-Containing Diatomic Molecules: Accurate Molecular Properties and the Great Lengths to Obtain Them

“…The spin states for the groups 3, 5, 6, and 7 molecules are consistent with a single bond with the Pd atom. However, the singlet ground state for PdC and PdSi suggests a double bond, which is consistent with the proposition of ref . We have further obtained the triplet energy for PdC at the CCSD­(T,CV)/aug-cc-pWCVQZ level and find that it is indeed higher in energy than the corresponding singlet.…”

“…The bond energies and the contributions from the various components are given in Table . For comparison, the table also contains available literature values for the bond energies, specifically for PdH, PdB, PdC, PdO, PdF, PdAl, PdSi, and Pd 2 . Among these, the ones for PdB, PdO, PdAl, PdSi, and Pd 2 are from the experiment, while the others are from computational studies with MRCI (for PdH, and PdC) or CISD (PdF).…”

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

“…Feature X, then, results from photodetachment from the 2p orbital, which for the PdC system, has been described as an anti-bonding orbital. 96 The 2 P state assignment is also in line with the PdSi À ground state calculations performed by Wu and Su. 16 Furthermore, the calculated bond distance decreases by 0.048 Å (UB3LYP/mixed basis set) when going from the anion ground state to the neutral ground state.…”

“…The narrow photoelectron signal of feature A of the PdSi À binding energy spectrum is usually attributed to photodetachment from a non-bonding orbital. 74 When comparing with the valence orbital configuration of PdC, 96 the 3s valence orbital is described as a non-bonding orbital localized on Pd and detachment of an electron from this orbital will cause minimal disturbance to the electronic structure of the diatomic (as revealed by the narrow feature A of PdSi À binding energy spectrum in Fig. 1).…”

DAPD Set of Pd-Containing Diatomic Molecules: Accurate Molecular Properties and the Great Lengths to Obtain Them

“…The spin states for the groups 3, 5, 6, and 7 molecules are consistent with a single bond with the Pd atom. However, the singlet ground state for PdC and PdSi suggests a double bond, which is consistent with the proposition of ref . We have further obtained the triplet energy for PdC at the CCSD­(T,CV)/aug-cc-pWCVQZ level and find that it is indeed higher in energy than the corresponding singlet.…”

“…The bond energies and the contributions from the various components are given in Table . For comparison, the table also contains available literature values for the bond energies, specifically for PdH, PdB, PdC, PdO, PdF, PdAl, PdSi, and Pd 2 . Among these, the ones for PdB, PdO, PdAl, PdSi, and Pd 2 are from the experiment, while the others are from computational studies with MRCI (for PdH, and PdC) or CISD (PdF).…”

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

“…Feature X, then, results from photodetachment from the 2p orbital, which for the PdC system, has been described as an anti-bonding orbital. 96 The 2 P state assignment is also in line with the PdSi À ground state calculations performed by Wu and Su. 16 Furthermore, the calculated bond distance decreases by 0.048 Å (UB3LYP/mixed basis set) when going from the anion ground state to the neutral ground state.…”

“…The narrow photoelectron signal of feature A of the PdSi À binding energy spectrum is usually attributed to photodetachment from a non-bonding orbital. 74 When comparing with the valence orbital configuration of PdC, 96 the 3s valence orbital is described as a non-bonding orbital localized on Pd and detachment of an electron from this orbital will cause minimal disturbance to the electronic structure of the diatomic (as revealed by the narrow feature A of PdSi À binding energy spectrum in Fig. 1).…”

DAPD Set of Pd-Containing Diatomic Molecules: Accurate Molecular Properties and the Great Lengths to Obtain Them

“…The spin states for the groups 3, 5, 6, and 7 molecules are consistent with a single bond with the Pd atom. However, the singlet ground state for PdC and PdSi suggests a double bond, which is consistent with the proposition of ref . We have further obtained the triplet energy for PdC at the CCSD­(T,CV)/aug-cc-pWCVQZ level and find that it is indeed higher in energy than the corresponding singlet.…”

“…The bond energies and the contributions from the various components are given in Table . For comparison, the table also contains available literature values for the bond energies, specifically for PdH, PdB, PdC, PdO, PdF, PdAl, PdSi, and Pd 2 . Among these, the ones for PdB, PdO, PdAl, PdSi, and Pd 2 are from the experiment, while the others are from computational studies with MRCI (for PdH, and PdC) or CISD (PdF).…”

Probing the valence orbitals of transition metal–silicon diatomic anions: ZrSi, NbSi, MoSi, PdSi and WSi

“…Feature X, then, results from photodetachment from the 2p orbital, which for the PdC system, has been described as an anti-bonding orbital. 96 The 2 P state assignment is also in line with the PdSi À ground state calculations performed by Wu and Su. 16 Furthermore, the calculated bond distance decreases by 0.048 Å (UB3LYP/mixed basis set) when going from the anion ground state to the neutral ground state.…”

“…The narrow photoelectron signal of feature A of the PdSi À binding energy spectrum is usually attributed to photodetachment from a non-bonding orbital. 74 When comparing with the valence orbital configuration of PdC, 96 the 3s valence orbital is described as a non-bonding orbital localized on Pd and detachment of an electron from this orbital will cause minimal disturbance to the electronic structure of the diatomic (as revealed by the narrow feature A of PdSi À binding energy spectrum in Fig. 1).…”