The carbon-nitrogen bond energy in tert-butyldifluoroamine

Pepkin, V. I.; Lebedev, Yu. A.; Novoselov, N. P.; Kosyrev, Yu. M.; Фокин, А. В.; Apin, A. Ya.

doi:10.1007/bf00910850

Cited by 3 publications

(4 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The AREP- and REP-optimized geometries at the HF level of theory are listed in Table . The REP bond lengths of XeF 2 and XeF 4 are 1.975 and 1.939 Å, respectively, which are shorter than the DHF values, 2.004 and 1.969 Å, by about 0.03 Å, but are in good agreement with the experimental data − of 1.977 and 1.95 Å. The bond lengths using scalar relativistic ECPs by Dolg et al are 2.067 and 2.025 Å for RnF 2 and RnF 4 , respectively, which are in very good agreement with the present AREP values, although they used large-core 8VE−ECPs.…”

Section: Resultssupporting

confidence: 88%

“…The AREP-and REP-optimized geometries at the HF level of theory are listed in Table 1. The REP bond lengths of XeF 2 and XeF 4 are 1.975 and 1.939 Å, respectively, which are shorter than the DHF values, 2.004 and 1.969 Å, by about 0.03 Å, but are in good agreement with the experimental data [32][33][34] The structural changes due to spin-orbit interactions for Xe fluorides are negligible and those for Rn and (118) fluorides are modest. The spin-orbit coupling elongates the Rn-F bond lengths by about 0.02 Å and the (118)-F ones by about 0.05 Å (Table 1).…”

Section: Resultssupporting

confidence: 80%

See 1 more Smart Citation

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄

Han

Lee

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

Ab initio calculations of RgF n (Rg = Xe, Rn, and Element 118; n = 2, 4) were performed using relativistic effective core potentials and two-component HF, MP2, CCSD, and CCSD(T) methods. Geometries were optimized at the HF level with and without effective spin−orbit operators. The D 4 h structures of all tetrafluorides and the linear difluorides are local minima with and without spin−orbit interactions. Spin−orbit contributions makes the T d form of (118)F4 another local minimum with the energy comparable to that of the D 4 h one. The spin−orbit interactions stabilize the (118) fluorides by a significant margin (∼2.0 eV) and the Rn fluorides by 40−60% (0.2∼ 0.4 eV) of the stabilization energy obtained at the corresponding scalar relativistic level. For (118)F4, the vibrational frequency of the B2u mode of the D 4 h form decreases from 143 to 20 cm-1 upon inclusion of the spin−orbit interactions, and a doubly degenerate mode of the T d structure, which is stable only with the inclusion of spin−orbit interactions, has the frequency of 34 cm-1, indicating that the (118)F4 molecule is very flexible due to spin−orbit effects.

show abstract

Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 80%

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄

Han

Lee

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…As articulated in the Rundle–Pimentel model, these molecules, which are referred to as “hypervalent”, involve 3‐center, 4‐electron (3c/4e) bonds, which increase the coordination number of the central atom in formal violation of the Octet Rule. Xenon difluoride, XeF 2 , is a prototypical hypervalent molecule, having a linear F−Xe−F structure, which involves a 3c/4e bond with a strength of 64.1 kcal mol −1 relative to the dissociation limit, despite the fact that Xe is a noble gas.…”

Section: Charge‐shift Bonding In Hypervalent (Three‐center Four‐electron) Systemsmentioning

confidence: 99%

Charge‐Shift Bonding: A New and Unique Form of Bonding

et al. 2019

View full text Add to dashboard Cite

Stichwçrter: bond theory ·charge-shift bonds · covalent bonds ·ionic bonds ·v alence bonds Dedicated to Roald HoffmannAbstract: Charge-shift bonds (CSBs) constitute anew class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures.T his Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus,v alence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as av ariety of electron density theories all show the distinction of CSBs vis-à-vis covalent and ionic bonds. Furthermore,t he covalent-ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules,e .g., benzene. The Essaye nds by arguing that CSBs are ad istinct family of bonding,w ith ap otential to bring about aR enaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.

show abstract

“…This change in electronic structure is also seen of course in the TCSCF potential curve in Figure a The different types of wave functions are described in the text. 6 Reference 7. c Reference 6.…”

Section: Electronic Structure Considerationsmentioning

confidence: 99%

Electron correlation and the reality of xenon difluoride

Bagus¹,

Liu²,

Liskow³

et al. 1975

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The electronic structure of xenon difluoride has been studied using ab initio theoretical methods. The primary goal was to determine whether current theoretical methods are capable of yielding a reasonable value of the dissociation energy of XeF2. A Slater function basis set of slightly better than "double [ plus polarization" quality was employed. Four different types of wave functions were investigated: two-configuration SCF, full valence configuration interaction (CI), the first-order wave function, and a larger 1234 configuration wave function including all double excitation from the loa, orbital. Although the TCSCF symmetric stretching potential curve has both a minimum and maximum, the minimum lies above the comparable energy of separated Xe + 2F. However, the two most complete wave functions predict dissociation energies of 1.97 and 2.14 e", in qualitative agreement with experiment, 2.78 eV. All four wave functions provide good predictions of the Xe-F equilibrium bond distance. As was the case for KrF2, the bonding in XeF2 is found to conform quite closely to Coulson's model F Xe+ F--F-Xe+ F near the equilibrium geometry, The role of the "outer orbitals" 5d and 4f appears to be a quantitative rather than qualitative one.Xenon difluoride appears to be the simplest known Xecontaining molecule, although there is still some controversy2 concerning the existence of the XeF radical. As such, XeF2 plays a special role in the chemistry of the noble gases.' XeF2 was first prepared4 in 1962, shortly after Bartlett's discovery5 of XePtF6, and several relatively simple methods of preparation are now a~a i l a b l e .~ The dissociation energy for the process XeF2 -Xe + 2F is -64 kcal/mo16 = 2.78 eV. Assuming the value' 38.8 f 2.3 kcal/mol for the dissociation energy De of F2, the molecular dissociation energy for the process XeF2 -Xe + F2 is found to be -25 kcal/mol. For comparison, the smaller KrF2 molecule is known to lie energetically aboue (by -15 kcal/mol) the analogous dissociation limit Kr + F2. This difference between KrF2 and XeF2 explains the transient nature of the former as compared to the relative stability of the latter. The geometrical structure of XeF2 is known from infrared and Raman studies to be linear and ~y m m e t r i c ,~ corresponding to point group Dmh. Reichman and Schreinerg have determined the gas-phase Xe-F bond distance to be 1.977 f 0.002

show abstract

The carbon-nitrogen bond energy in tert-butyldifluoroamine

Cited by 3 publications

References 1 publication

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄

Charge‐Shift Bonding: A New and Unique Form of Bonding

Electron correlation and the reality of xenon difluoride

Contact Info

Product

Resources

About

The carbon-nitrogen bond energy in tert-butyldifluoroamine

Cited by 3 publications

References 1 publication

Structures of RgFn (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F4

Structures of RgFn (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F4

Charge‐Shift Bonding: A New and Unique Form of Bonding

Electron correlation and the reality of xenon difluoride

Contact Info

Product

Resources

About

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄

Structures of RgF_n (Rg = Xe, Rn, and Element 118. n = 2, 4.) Calculated by Two-component Spin−Orbit Methods. A Spin−Orbit Induced Isomer of (118)F₄