Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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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 - 2019/12/15
Y1 - 2019/12/15
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
KW - NUCLEAR-MAGNETIC-RESONANCE
KW - AB-INITIO
KW - ROTATIONAL SPECTRUM
KW - INFRARED-SPECTRA
KW - BIFLUORIDE ION
KW - GAS-PHASE
KW - ELECTRON-DENSITY PROPERTIES
KW - DIODE-LASER SPECTROSCOPY
KW - VIBRATIONAL DYNAMICS
KW - PHOTOELECTRON-SPECTROSCOPY
UR - http://www.scopus.com/inward/record.url?scp=85072207966&partnerID=8YFLogxK
UR - http://www.mendeley.com/research/anticooperativity-fhcl-hydrogen-bonds-fhncl-clusters-n-16
U2 - 10.1002/jcc.26066
DO - 10.1002/jcc.26066
M3 - Article
C2 - 31506964
AN - SCOPUS:85072207966
VL - 40
SP - 2858
EP - 2867
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 32
ER -
ID: 48655717