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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.

In: Journal of Computational Chemistry, Vol. 40, No. 32, 15.12.2019, p. 2858-2867.

Research output: Contribution to journal › Article › peer-review

Harvard

Tupikina, EY, Denisov, GS & Tolstoy, PM 2019, 'Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)', Journal of Computational Chemistry, vol. 40, no. 32, pp. 2858-2867. https://doi.org/10.1002/jcc.26066

APA

Tupikina, E. Y., Denisov, G. S., & Tolstoy, P. M. (2019). Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6). Journal of Computational Chemistry, 40(32), 2858-2867. https://doi.org/10.1002/jcc.26066

Vancouver

Tupikina EY, Denisov GS, Tolstoy PM. Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6). Journal of Computational Chemistry. 2019 Dec 15;40(32):2858-2867. https://doi.org/10.1002/jcc.26066

Author

Tupikina, Elena Yu. ; Denisov, Gleb S. ; Tolstoy, Peter M. / Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6). In: Journal of Computational Chemistry. 2019 ; Vol. 40, No. 32. pp. 2858-2867.

BibTeX

@article{cf4fa0bbb07246fb8823ea035d8439d1,
title = "Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)",
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.",
keywords = "cooperativity, hydrogen bond energy, hydrogen bonds, nucleation, solvation, NUCLEAR-MAGNETIC-RESONANCE, AB-INITIO, ROTATIONAL SPECTRUM, INFRARED-SPECTRA, BIFLUORIDE ION, GAS-PHASE, ELECTRON-DENSITY PROPERTIES, DIODE-LASER SPECTROSCOPY, VIBRATIONAL DYNAMICS, PHOTOELECTRON-SPECTROSCOPY",
author = "Tupikina, {Elena Yu.} and Denisov, {Gleb S.} and Tolstoy, {Peter M.}",
year = "2019",
month = dec,
day = "15",
doi = "10.1002/jcc.26066",
language = "English",
volume = "40",
pages = "2858--2867",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "Wiley-Blackwell",
number = "32",

}

RIS

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