On the origin and nature of internal methyl rotation barriers: an information-theoretic approach study

Wang, Kedi; He, Xin; Rong, Chunying; Zhong, Aiguo; Liu, Shubin; Zhao, Dongbo

doi:10.1007/s00214-022-02910-9

Cited by 50 publications

(28 citation statements)

References 82 publications

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“…As shown in Figure , all the studied isomers exhibit a –CH 3 group, whose internal rotation, if feasible, will couple with the overall rotation of the molecule. This rotation phenomenon has relevant implications in the structure but also for the reactivity of the studied molecules . Particularly, depending on the magnitude of the V 3 torsional barrier height, this motion may originate sizable A – E torsional splittings (fine structure) in the rotational spectra corresponding to the ground state of the molecule, whose analysis will be essential to achieve a proper experimental characterization.…”

Section: Resultsmentioning

confidence: 99%

Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study

Sanz-Novo,

Redondo,

Sánchez

et al. 2024

J. Phys. Chem. A

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The exploration of phosphorus-bearing species stands as a prolific field in current astrochemical research, particularly within the context of prebiotic chemistry. Herein, we have employed high-level quantum chemistry methodologies to predict the structure and spectroscopic properties of isomers composed of a methyl group and three P, C, and O atoms. We have computed relative and dissociation energies, as well as rotational, rovibrational, and torsional parameters using the B2PLYPD3 functional and the explicitly correlated coupled cluster CCSD(T)-F12b method. Based upon our study, all the isomers exhibit a bent heavy atom skeleton with CH3PCO being the most stable structure, regardless of the level theory employed. Following in energy, we found four high-energy isomers, namely, CH3OCP, CH3CPO, CH3COP, and CH3OPC. The computed adiabatic dissociation energies support the stability of all [CH3, P, C, O] isomers against fragmentation into CH3 and [P, C, O]. Torsional barrier heights associated with the methyl internal rotation for each structure have been computed to evaluate the occurrence of possible A–E splittings in the rotational spectra. For the most stable isomer, CH3PCO, we found a V 3 barrier of 82 cm–1, which is slightly larger than that obtained experimentally for the N-counterpart, CH3NCO, yet still very low. Therefore, the analysis of its rotational spectrum can be anticipated as a challenging task owing to the effect of the CH3 internal rotation. The complete set of spectroscopic constants and transition frequencies reported here for the most stable isomer, CH3PCO, is intended to facilitate eventual laboratory searches.

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Section: Resultsmentioning

confidence: 99%

Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study

Sanz-Novo,

Redondo,

Sánchez

et al. 2024

J. Phys. Chem. A

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“…For pseudopotential calculations, the electron density functions (EDFs) [64] were applied for core electron modeling. The electron localization function (ELF) [65][66][67] and one-electron potential (OEP) [68,69] projection analysis, Bader [70][71][72] atoms-in-molecules topological analysis of electron density (QTAIM) [73], electron density difference (EDD) [74][75][76][77][78] projections, and electron density/electrostatic potential (ED/ESP) profile analysis [79] were performed and visualized in Multiwfn 3.8 [41,80,81]. The analysis of the electrostatic surface (ρ = 0.001 e/bohr 3 ) [82] potentials [83][84][85] (ESP) was carried out for isolated molecules in Multiwfn 3.8 and visualized in VMD 1.9.3.…”

Section: Computational Detailsmentioning

confidence: 99%

“…[ [70][71][72] atoms-in-molecules topological analysis of electron density (QTAIM) [73], electron density difference (EDD) [74][75][76][77][78] projections, and electron density/electrostatic potential (ED/ESP) profile analysis [79] were performed and visualized in Multiwfn 3.8 [41,80,81]. The analysis of the electrostatic surface (ρ = 0.001 e/bohr 3 ) [82] potentials [83][84][85] (ESP) was carried out for isolated molecules in Multiwfn 3.8 and visualized in VMD 1.9.3.…”

Section: Electrostatic Surface Potentialsmentioning

confidence: 99%

Metal-Involving Halogen Bonding Confirmed Using DFT Calculations with Periodic Boundary Conditions

et al. 2023

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The cocrystallization of trans-[PtI2(NCN(CH2)5)2] and iodoform (CHI3) yields crystalline adduct trans-[PtI2(NCN(CH2)5)2]∙2CHI3, the structure of which was studied via single-crystal X-ray diffractometry (XRD). In the XRD structure of trans-[PtI2(NCN(CH2)5)2]∙2CHI3, apart from rather predictable C–H∙∙∙I hydrogen bonds (HBs) and C−I∙∙∙I halogen bonds (XBs) with the iodide ligands, we identified C–I∙∙∙Pt metal-involving XBs, where the platinum center functions as an XB acceptor (that includes a metal dz2-orbital) toward the σ-holes of I atoms of CHI3. DFT calculations (PBE-D3/jorge-TZP-DKH with plane waves in the GAPW method) were carried out in the CP2K program for isolated molecules, complex–iodoform clusters, and crystal models with periodic boundary conditions, where the noncovalent nature and the existence of the interactions were confirmed using charge analysis, Wiberg bond indexes, and QTAIM topology analysis of electron density, whereas the philicities of the noncovalent partners were proved using charge analysis, electron localization function, electron density deformation, and one-electron potential projections, as well as electron density/electrostatic potential profiles for cluster models and electrostatic potential surfaces (ρ = 0.001 a.u.) for isolated molecules.

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“…The nature of the intermolecular interactions can be quantified using an HS investigation. 25,26 Based on the final X-ray refinement results imported from CIF (Crystallographic Information File) formats, the Hirshfeld surfaces of 2D fingerprint plots were calculated using the Crystal Explorer program. The crucial Hirshfeld surface analysis output, namely, the d norm plot, constructed between −0.5 and 1.5 displayed red depressions indicative of interaction in crystal packing.…”

Section: Magnetic Propertiesmentioning

confidence: 99%

Structures and magnetic studies of four new Ni(ii) coordination polymers built using symmetrical tetracarboxylate and N-donor linkers

Zhang,

Qin,

Liu

et al. 2023

New J. Chem.

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On the origin and nature of internal methyl rotation barriers: an information-theoretic approach study

Cited by 50 publications

References 82 publications

Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study

Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study

Metal-Involving Halogen Bonding Confirmed Using DFT Calculations with Periodic Boundary Conditions

Structures and magnetic studies of four new Ni(ii) coordination polymers built using symmetrical tetracarboxylate and N-donor linkers

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On the origin and nature of internal methyl rotation barriers: an information-theoretic approach study

Cited by 50 publications

References 82 publications

Structure and Spectroscopic Insights for CH3PCO Isomers: A High-Level Quantum Chemical Study

Structure and Spectroscopic Insights for CH3PCO Isomers: A High-Level Quantum Chemical Study

Metal-Involving Halogen Bonding Confirmed Using DFT Calculations with Periodic Boundary Conditions

Structures and magnetic studies of four new Ni(ii) coordination polymers built using symmetrical tetracarboxylate and N-donor linkers

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Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study

Structure and Spectroscopic Insights for CH₃PCO Isomers: A High-Level Quantum Chemical Study