PCCP and its isomers: a theoretical studyElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b106927f/

Hajgató, Balázs; Tran, Phuong Hoang; Veszprémi, Tamás; Nguyen, Minh Tho

doi:10.1039/b106927f

Cited by 11 publications

(6 citation statements)

References 38 publications

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“…Previous studies have reported a disagreement between theory and experiment for the heat of formation of CP. − The calculated Δ f H °(0 K) values for CP124.1 kcal/mol (DFT), 127.3 kcal/mol (CASPT2), and 121.0 kcal/mol (G3B3)are in good agreement with the best computational heat of formation (124 ± 2 kcal/mol). The variation between the CASPT2 and G3B3 calculations for the heats of formation (0 K) of CP (6.3 kcal/mol) and BP (5.7 kcal/mol) can be attributed largely to the empirical HLC in the G3B3 method.…”

Section: Resultssupporting

confidence: 57%

“…Interest in CP has been sparked by the discovery of CP in the inner layers of the carbon star envelope IRC+10216 . In addition, a serious deviation between the calculated heat of formation (Δ f H °) of CP and the experimental values in the NIST Webbook has been discovered. − Now, it is accepted that the recommended value for Δ f H ° (0 K) of CP is ∼124 kcal/mol, rather than 106 kcal/mol.…”

Section: Introductionmentioning

confidence: 99%

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An Investigation of the BCP Potential Energy Surface

Joo

McKee

2004

J. Phys. Chem. A

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The singlet and triplet potential energy surfaces (PESs) of boron−carbon−phosphorus (BCP) isomers were investigated, using various theoretical methods. Geometries of the minima and transition states on the PES were optimized at the B3LYP/6-311+G(2df) and CASSCF(12,12)/6-311+G(2df) levels, and single-point calculations were made at the CASPT2/ANO-L level, to consider dynamic electron correlation effects. The most-stable isomer was linear singlet BCP (1Σ+); its calculated heat of formation (Δf H°, 0 K) is 150.5 ± 2 kcal/mol. Study of the fragmentation processes in BCP revealed that the bond enthalpies of the B−C and C−P bonds in BCP (1Σ+) at 0 K are 111.7 and 128.9 kcal/mol, respectively, at the CASPT2/ANO-L level. A possible crossing mechanism between two electronic states (3A‘ and 3A‘ ‘) is discussed, and Renner−Teller species with 3Π state symmetry are investigated.

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Section: Resultssupporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

An Investigation of the BCP Potential Energy Surface

Joo

McKee

2004

J. Phys. Chem. A

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“…The only reported work on diphosphaalkynes has focused on the smallest member of the series, PCCP, the phosphorus analogue of the well-studied NCCN. − The calculated geometry of the ground and lowest excited states as well as the predicted photoelectron spectra were consistent 19 with the physical property information provided above and were, therefore, different from the related data available for the nitrogen analogue. The existence of the PCCP molecule was later confirmed by a neutralization−reionization mass spectrometric investigation, but this experiment could not, by its nature, provide any structural information.…”

Section: Introductionmentioning

confidence: 82%

“…The existence of the PCCP molecule was later confirmed by a neutralization−reionization mass spectrometric investigation, but this experiment could not, by its nature, provide any structural information. A later, computational study considered all of the possible PCCP isomers and concluded that the lowest conformer was the linear form terminated by phosphorus atoms …”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory Study of the Electronic State, Geometry, and Harmonic Frequencies for Linear C_nP₂ Clusters: A Comparison with C_nN₂

Chuchev

BelBruno

2003

J. Phys. Chem. A

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Linear C n N2 and C n P2 clusters, in the lowest energy singlet and triplet states, were studied using the B3LYP/ 6-311G** theoretical method for n = 5−10 and the B3LYP/aug-cc-pVTZ method for n = 5−8. Harmonic frequencies are also reported. Clusters with odd numbers of carbon atoms have lower lying triplet ground states, while those with even numbers of carbons are singlets. The energies of the acetylenic singlet ground states are approximately 2.5 eV below those of the lowest triplet state, while the triplet ground states tend to be more cumulenic and are preferred by 0.6−0.8 eV. A comparison of the properties of the di-heteroatom terminated clusters, on the basis of the atomic properties of nitrogen and phosphorus, is presented. Some important differences in molecular properties are highlighted.

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“…These values, however, are entirely consistent with CCSD(T) optimizations with correlation consistent triple-ζ basis sets. 71 Potential energy curves (PECs) of the dimer structures were computed in three different configurations: cross (X), paralleldisplaced (PD), and T-shaped (T) that belong to the D 2d , C 2h , and C 2v point groups, respectively. These configurations are depicted in Figure 1 for (PCCP) 2 , but the general definitions of the intermolecular geometrical parameters also apply to (P 2 ) 2 and (NCCN) 2 .…”

Section: Methodsmentioning

confidence: 99%

Accurate Interaction Energies for Problematic Dispersion-Bound Complexes: Homogeneous Dimers of NCCN, P₂, and PCCP

Hohenstein

Jaeger

Carrell

et al. 2011

J. Chem. Theory Comput.

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All intermolecular interactions involve London dispersion forces. The accurate treatment of dispersion is essential for the computation of realistic interaction potentials. In general, the most reliable method for computing intermolecular interactions is coupled-cluster singles and doubles with perturbative triples [CCSD(T)] in conjunction with a sufficiently flexible Gaussian atomic orbital basis set, a combination which is not routinely applicable due to its excessive computational demands (CPU time, memory, storage). Recently, many theoretical methods have been developed that attempt to account for dispersion in a more efficient manner. It is well-known that dispersion interactions are more difficult to compute in some systems than others; for example, π-π dispersion is notoriously difficult, while alkane-alkane dispersion is relatively simple to compute. In this work, numerous theoretical methods are tested for their ability to compute reliable interaction energies in particularly challenging systems, namely, the P2, PCCP, and NCCN dimers. Symmetry-adapted perturbation theory (SAPT) is applied to these dimers to demonstrate their sensitivity to the treatment of dispersion. Due to the small size of these systems, highly accurate CCSD(T) potential energy curves could be estimated at the complete basis set limit. Numerous theoretical methods are tested against the reliable CCSD(T) benchmarks. Methods using a treatment of dispersion that relies on time-dependent density functional theory (TDDFT) response functions are found to be the most reliable.

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PCCP and its isomers: a theoretical studyElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b106927f/

Cited by 11 publications

References 38 publications

An Investigation of the BCP Potential Energy Surface

An Investigation of the BCP Potential Energy Surface

Density Functional Theory Study of the Electronic State, Geometry, and Harmonic Frequencies for Linear C_nP₂ Clusters: A Comparison with C_nN₂

Accurate Interaction Energies for Problematic Dispersion-Bound Complexes: Homogeneous Dimers of NCCN, P₂, and PCCP

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PCCP and its isomers: a theoretical studyElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b106927f/

Cited by 11 publications

References 38 publications

An Investigation of the BCP Potential Energy Surface

An Investigation of the BCP Potential Energy Surface

Density Functional Theory Study of the Electronic State, Geometry, and Harmonic Frequencies for Linear CnP2 Clusters: A Comparison with CnN2

Accurate Interaction Energies for Problematic Dispersion-Bound Complexes: Homogeneous Dimers of NCCN, P2, and PCCP

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Density Functional Theory Study of the Electronic State, Geometry, and Harmonic Frequencies for Linear C_nP₂ Clusters: A Comparison with C_nN₂

Accurate Interaction Energies for Problematic Dispersion-Bound Complexes: Homogeneous Dimers of NCCN, P₂, and PCCP