Anticooperativity of FH···Cl hydrogen bonds in [FH)nCl] clusters (n = 1…6)

Elena Yu. Tupikina, Gleb S. Denisov, Peter M. Tolstoy

Результат исследований: Научные публикации в периодических изданияхстатья

Выдержка

The change of cooperativity of FH···Cl hydrogen bonds upon sequential addition of up to six FH molecules to the Cl first coordination sphere is investigated. The geometry of clusters [(FH)nCl] (n = 1…6) was calculated (CCSD/aug-cc-pVDZ) and compared with [(FH)nF] clusters. The geometry is determined by the symmetry-driven electrostatic requirements and also by the fact that formation of each new FH···Cl bond creates a depression in the chlorine's electron cloud on the opposite side of Cl (σ-hole), which limits the range of directions available for subsequent H-bond formation. The mutual influence of FH···Cl hydrogen bonds is anticooperative—the addition of each FH molecule weakens H-bonds by 23–16% and decreases their covalent character (as seen by LMO-EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl.

Язык оригиналаанглийский
Страницы (с-по)2858-2867
ЖурналJournal of Computational Chemistry
Том40
Номер выпуска32
Ранняя дата в режиме онлайн10 сен 2019
DOI
СостояниеЭлектронная публикация перед печатью - 10 сен 2019

Отпечаток

Hydrogen Bonds
Hydrogen bonds
Molecules
Geometry
Chlorine
Chemical shift
Electrostatics
Electron
Decomposition
Symmetry
Decompose
Decrease
Electrons
Requirements
Range of data
Character
Influence
Direction compound

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  • Вычислительная математика

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abstract = "The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH)nCl]− (n = 1…6) was calculated (CCSD/aug-cc-pVDZ) and compared with [(FH)nF]− clusters. The geometry is determined by the symmetry-driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ-hole), which limits the range of directions available for subsequent H-bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H-bonds by 23–16{\%} and decreases their covalent character (as seen by LMO-EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl.",
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Anticooperativity of FH···Cl hydrogen bonds in [FH)nCl] clusters (n = 1…6). / Tupikina, Elena Yu.; Denisov, Gleb S.; Tolstoy, Peter M.

В: Journal of Computational Chemistry, Том 40, № 32, 15.12.2019, стр. 2858-2867.

Результат исследований: Научные публикации в периодических изданияхстатья

TY - JOUR

T1 - Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

AU - Tupikina, Elena Yu.

AU - Denisov, Gleb S.

AU - Tolstoy, Peter M.

PY - 2019/9/10

Y1 - 2019/9/10

N2 - The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH)nCl]− (n = 1…6) was calculated (CCSD/aug-cc-pVDZ) and compared with [(FH)nF]− clusters. The geometry is determined by the symmetry-driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ-hole), which limits the range of directions available for subsequent H-bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H-bonds by 23–16% and decreases their covalent character (as seen by LMO-EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl.

AB - The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH)nCl]− (n = 1…6) was calculated (CCSD/aug-cc-pVDZ) and compared with [(FH)nF]− clusters. The geometry is determined by the symmetry-driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ-hole), which limits the range of directions available for subsequent H-bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H-bonds by 23–16% and decreases their covalent character (as seen by LMO-EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl.

KW - cooperativity

KW - hydrogen bond energy

KW - hydrogen bonds

KW - nucleation

KW - solvation

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