A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N<sub>2</sub>

McDowell, Sean A. C.

doi:10.1002/jcc.20792

Cited by 7 publications

(2 citation statements)

References 33 publications

(67 reference statements)

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“…Most 3D quantum chemical procedures follow the super-molecular approach, calculating optimized geometries and interaction energies of H bond donor-acceptor complexes. [13][14][15][16][17][18] With this approach, however, it is difficult to extract individual contributions from the atomic sites participating in H-bonding.…”

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confidence: 99%

Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

et al. 2008

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A quantum chemical model is introduced to predict the H-bond donor strength of monofunctional organic compounds from their ground-state electronic properties. The model covers -OH, -NH, and -CH as H-bond donor sites and was calibrated with experimental values for the Abraham H-bond donor strength parameter A using the ab initio and density functional theory levels HF/6-31G** and B3LYP/6-31G**. Starting with the Morokuma analysis of hydrogen bonding, the electrostatic (ES), polarizability (PL), and charge transfer (CT) components were quantified employing local molecular parameters. With hydrogen net atomic charges calculated from both natural population analysis and the ES potential scheme, the ES term turned out to provide only marginal contributions to the Abraham parameter A, except for weak hydrogen bonds associated with acidic -CH sites. Accordingly, A is governed by PL and CT contributions. The PL component was characterized through a new measure of the local molecular hardness at hydrogen, eta(H), which in turn was quantified through empirically defined site-specific effective donor and acceptor energies, EE(occ) and EE(vac). The latter parameter was also used to address the CT contribution to A. With an initial training set of 77 compounds, HF/6-31G** yielded a squared correlation coefficient, r(2), of 0.91. Essentially identical statistics were achieved for a separate test set of 429 compounds and for the recalibrated model when using all 506 compounds. B3LYP/6-31G** yielded slightly inferior statistics. The discussion includes subset statistics for compounds containing -OH, -NH, and active -CH sites and a nonlinear model extension with slightly improved statistics (r(2) = 0.92).

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Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

et al. 2008

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“…When the basis set varies from 311++G(d,p) to 6-311++G(2d,2p), the binding distance ( R st ) is from 1.8632 Å to 1.9322 Å, the change of the H−Ar bond length (Δ r st ) is from −0.0924 Å to −0.1013 Å, the frequency shift of the H−Ar stretch (Δ v st ) is from 567 cm −1 to 553 cm −1 , the IR intensity of the H−Ar stretch ( I st ) is from 979 km/mol to 447 km/mol, the interaction energy (Δ E st ) is from −9.99 to −11.80 kJ/mol, and the dipole moment is from 14.716 to 13.317 D. These changes indicate that the C 2 H 2 ···HArCCF complex is weakly combined. The 6-311++G(2d,2p) basis set was often used to descript the structure and properties of hydrogen-bonded complexes involving a noble-gas atom, thus it is also adopted in this article.…”

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Gigantic Blue Shift of the H−Ar Stretch Vibration in π Hydrogen-Bonded C₂H₂···HArCCF Complex

et al. 2009

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Quantum chemical calculations have been performed to study the structure and properties of the pi hydrogen-bonded complex formed between acetylene and HArCCF at the MP2/6-311++G(2d,2p) level. The C(2)H(2)...HCCF and C(2)H(2)...HCCArF complexes were also studied for comparison with the C(2)H(2)...HArCCF complex. The basis set superposition errors (BSSE)-counterpoise corrected potential-energy surface (PES) has a larger influence on the structure and properties of the C(2)H(2)...HArCCF complex than those of the C(2)H(2)...HCCF and C(2)H(2)...HCCArF complexes. The C(2)H(2)...HArCCF complex exhibits a very large harmonic vibrational frequency blue shift of 574 cm(-1) for the H-Ar stretch, whereas the C(2)H(2)...HCCF and C(2)H(2)...HCCArF complexes exhibit a small red shift of 35 and 47 cm(-1) for the H-C stretch, respectively; upon complexation the IR intensity decreases in the former, whereas it increases in the latter. The origin of the frequency shift and nature of the hydrogen bond in these complexes have been unveiled with the natural bond orbital analysis and energy decomposition.

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Quantitative relationships between bond lengths, stretching vibrational frequencies, bond force constants, and bond orders in the hydrogen-bonded complexes involving hydrogen halides

Yang

Bai

et al. 2017

Struct Chem

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A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N₂

Cited by 7 publications

References 33 publications

Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

Gigantic Blue Shift of the H−Ar Stretch Vibration in π Hydrogen-Bonded C₂H₂···HArCCF Complex

Quantitative relationships between bond lengths, stretching vibrational frequencies, bond force constants, and bond orders in the hydrogen-bonded complexes involving hydrogen halides

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A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N2

Cited by 7 publications

References 33 publications

Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

Modeling the H bond donor strength of OH, NH, and CH sites by local molecular parameters

Gigantic Blue Shift of the H−Ar Stretch Vibration in π Hydrogen-Bonded C2H2···HArCCF Complex

Quantitative relationships between bond lengths, stretching vibrational frequencies, bond force constants, and bond orders in the hydrogen-bonded complexes involving hydrogen halides

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A comparative study of some red‐ and blue‐shifted linear H‐bonded complexes of N₂

Gigantic Blue Shift of the H−Ar Stretch Vibration in π Hydrogen-Bonded C₂H₂···HArCCF Complex