The quantum-chemical calculation of NMR indirect spin–spin coupling constants

Helgaker, Trygve; Jaszuński, Michał; Pecul, Magdalena

doi:10.1016/j.pnmrs.2008.02.002

Cited by 266 publications

(267 citation statements)

References 263 publications

(316 reference statements)

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“…[24] Optimized gasphase geometries at the B3LYP/6-311+g(d,p) level of theory were found to be minima by the absence of imaginary frequencies. NMR spectroscopic parameters (nuclear magnetic shielding by the gauge including atomic orbitals (GIAO) method, [25] and spin-spin coupling constants [26] ) were calculated at the same level of theory. …”

Section: Methodsmentioning

confidence: 99%

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations

2011

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The reaction of the diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion with BF 3 -OEt 2 affords selectively a spirocyclic bis(1,2-dicarba-closo-dodecaborane-1,2-diselena)-borate, whereas the analogous reaction with boron trichloride leads mainly to 1,2-bis(ethylseleno)-1,2-dicarba-closododecaborane(12) through ether cleavage. The spirocyclic borate reacts with methanol by cleavage of both Se-B and Se-C bonds. With borane in THF (BH 3 /THF) and also with LiBH 4 exchange reactions take place, which afford the 1,2-

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Section: Methodsmentioning

confidence: 99%

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations

2011

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“…Spin-spin coupling constants depend strongly on the nuclear positions, which means that they often have large vibrational contributions and exhibit a strong temperature dependence [8,40]. Consequently, particularly the zero-point vibrational (ZPV) corrections cannot be neglected when a comparison with experimental data is made.…”

Section: Vibrational Effectsmentioning

confidence: 99%

“…The ZPV correction to a given property can be calculated from the expectation value of this property over the vibrational ground-state wave function, therefore calculating vibrational corrections to the coupling constants for polyatomic molecules is computationally demanding. Thus, it becomes cost-effective to calculate the equilibrium values of the coupling constants at an advanced level of theory, and then estimate the vibrational corrections at a less expensive level, for instance DFT [8]. We use here such a simplified approach, vibrationally averaging spin-spin coupling constants at the nonrelativistic DFT level and then comparing the dependence of the coupling constants on selected geometry parameters as calculated with nonrelativistic and relativistic Hamiltonians.…”

Section: Vibrational Effectsmentioning

confidence: 99%

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

2018

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The nuclear spin-spin coupling constants in a series of acetylene derivatives HC≡CXH 3 , where X is C, Si, Ge, Sn, Pb, have been calculated employing both coupled-cluster theory (CC) and density functional theory (DFT), the latter in nonrelativistic and relativistic four-component approach with different exchange-correlation functionals and basis sets. In addition, property derivatives with respect to molecular geometry parameters have been computed with nonrelativistic and relativistic Hamiltonians in order to evaluate the usefulness of the calculated nonrelativistic vibrational corrections. Generally, the CC method reproduces the experimental values somewhat better than DFT. In the case of the latter, the performance of B3LYP functional was the most satisfactory. The relativistic effects become noticeable for the couplings including heavy atom in tin-and lead-containing molecules. The calculations of the derivatives of the coupling constants indicate that these derivatives are even more sensitive to the relativistic effects than the corresponding coupling constants.

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“…DFT provides such an alternative by inclusion of correlation effects in an approximate manner with modest computational costs. This is now accepted method for studying large molecules with non-negligible correlation effects, even though this method has its own shortcomings [17].…”

Section: Calculation Of Nmr Propertiesmentioning

confidence: 99%

Inverse hydrogen bond: theoretical investigation on the nature of interaction and spectroscopic properties

Ilnicka

Sadlej

2012

Struct Chem

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A computational investigation was carried out to characterize the inverse (hydride) hydrogen bond in model complexes. Properties such as molecular structures and energetics have been studied by supermolecular MP2 approach. We focus on vibrational spectra, NMR shielding, and spin-spin coupling constants-signals that reflect the electronic structures of the compounds. The bonding in these complexes has been analyzed for a first time by SymmetryAdapted Perturbation Theory to provide the intricate insight into the nature of the interaction. The cyclic complexes, which have multiple interaction, are stable due to strong redistribution of electron density upon the complexation and differ from the linear ones by the induction energy as the most important term exceeding the electrostatic term. The linear complexes, which represent the inverse hydrogen bond, are characterized by much stronger induction than dispersion energy, contrary to the conventional hydrogen bonds, where these two terms happen to be of nearly equal magnitude. This result is the most noticeable difference between inverse and conventional hydrogen bonds.

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The quantum-chemical calculation of NMR indirect spin–spin coupling constants

Cited by 266 publications

References 263 publications

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

Inverse hydrogen bond: theoretical investigation on the nature of interaction and spectroscopic properties

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The quantum-chemical calculation of NMR indirect spin–spin coupling constants

Cited by 266 publications

References 263 publications

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C2B10H10)Se2]2–: Structures, NMR Spectroscopy, and DFT Calculations

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C2B10H10)Se2]2–: Structures, NMR Spectroscopy, and DFT Calculations

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

Inverse hydrogen bond: theoretical investigation on the nature of interaction and spectroscopic properties

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A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations

A Spirocyclic Borate and a Dihydroborate Derived from the 1,2‐Diselenolato‐1,2‐dicarba‐closo‐dodecaborane(12) Dianion [1,2‐(1,2‐C₂B₁₀H₁₀)Se₂]^2–: Structures, NMR Spectroscopy, and DFT Calculations