TY - JOUR

T1 - Estimations of FH center dot center dot center dot X hydrogen bond energies from IR intensities

T2 - Iogansen's rule revisited

AU - Тупикина, Елена Юрьевна

AU - Толстой, Петр Михайлович

AU - Титова, Анна Александровна

AU - Костин, Михаил Александрович

AU - Денисов, Глеб Семенович

N1 - Publisher Copyright: © 2021 Wiley Periodicals LLC. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3/30

Y1 - 2021/3/30

N2 - In this work the possibility of using the IR intensity of the stretching vibration νs of proton donor group for estimation of hydrogen bond strength was investigated. For a set of complexes with FH···X (X = F, N, O) hydrogen bonds in the wide range of energies (0.1–49.2 kcal/mol) vibrational frequencies νs and their intensities A were calculated (CCSD at complete basis set limit). The validity of the previously proposed linear proportionality between the intensification of the stretching vibration νs in IR spectra and hydrogen bond enthalpy –ΔH = 12.2 urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0001 (A. V. Iogansen, Spectrochimica Acta A 1999) was examined. It is shown that for a range of similar hydrogen bond types with complexation energies ∆E <15 kcal/mol the ∆E(urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0002) function remains similar to that proposed in the Iogansen's work, while upon strengthening this dependency becomes significantly nonlinear. We examined two other parameters (urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0003 and urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0004) related to IR intensity as descriptors of hydrogen bond strength which are proportional to transition dipole moment matrix element and mass‐independent dipole moment derivative. It was found that the dependency ∆E(urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0005) stays linear in the whole studied range of complexation energies and it can be used for evaluation of ∆E from infrared spectral data with the accuracy about 2 kcal/mol. The mass‐independent product urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0006 is an appropriate descriptor for sets of complexes with various hydrogen bond types. Simple equations proposed in this work can be used for estimations of hydrogen bond strength in various systems, where experimental thermodynamic methods or direct calculations are difficult or even impossible.

AB - In this work the possibility of using the IR intensity of the stretching vibration νs of proton donor group for estimation of hydrogen bond strength was investigated. For a set of complexes with FH···X (X = F, N, O) hydrogen bonds in the wide range of energies (0.1–49.2 kcal/mol) vibrational frequencies νs and their intensities A were calculated (CCSD at complete basis set limit). The validity of the previously proposed linear proportionality between the intensification of the stretching vibration νs in IR spectra and hydrogen bond enthalpy –ΔH = 12.2 urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0001 (A. V. Iogansen, Spectrochimica Acta A 1999) was examined. It is shown that for a range of similar hydrogen bond types with complexation energies ∆E <15 kcal/mol the ∆E(urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0002) function remains similar to that proposed in the Iogansen's work, while upon strengthening this dependency becomes significantly nonlinear. We examined two other parameters (urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0003 and urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0004) related to IR intensity as descriptors of hydrogen bond strength which are proportional to transition dipole moment matrix element and mass‐independent dipole moment derivative. It was found that the dependency ∆E(urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0005) stays linear in the whole studied range of complexation energies and it can be used for evaluation of ∆E from infrared spectral data with the accuracy about 2 kcal/mol. The mass‐independent product urn:x-wiley:01928651:media:jcc26482:jcc26482-math-0006 is an appropriate descriptor for sets of complexes with various hydrogen bond types. Simple equations proposed in this work can be used for estimations of hydrogen bond strength in various systems, where experimental thermodynamic methods or direct calculations are difficult or even impossible.

KW - IR intensities

KW - IR spectroscopy

KW - hydrogen bond strength

KW - hydrogen bonds

KW - quantum-chemistry

UR - http://www.scopus.com/inward/record.url?scp=85099398126&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/dbcd2281-38e8-32af-a7c4-5faedd705cb6/

U2 - 10.1002/jcc.26482

DO - 10.1002/jcc.26482

M3 - Article

VL - 42

SP - 572

EP - 580

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 8

ER -