A Critical Overview of Current Theoretical Methods of Estimating the Energy of Intramolecular Interactions

Jabłoński, Mirosl̷aw

doi:10.3390/molecules25235512

Cited by 56 publications

(69 citation statements)

References 151 publications

(400 reference statements)

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“…Nevertheless, some empirical, semiempirical, and ab initio procedures [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ] have also been reported in the literature for estimating the IHB energy. These have been nicely summarized by Jablonski [ 40 ] in his article in this Special Issue, and we shall discuss only the aspects of these methods (e.g., their merits and demerits) that are not explicitly covered in Ref. [ 40 ].…”

Section: Introductionmentioning

confidence: 99%

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Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Deshmukh

Gadre

2021

Molecules

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Hydrogen bonds (HBs) play a crucial role in many physicochemical and biological processes. Theoretical methods can reliably estimate the intermolecular HB energies. However, the methods for the quantification of intramolecular HB (IHB) energy available in the literature are mostly empirical or indirect and limited only to evaluating the energy of a single HB. During the past decade, the authors have developed a direct procedure for the IHB energy estimation based on the molecular tailoring approach (MTA), a fragmentation method. This MTA-based method can yield a reliable estimate of individual IHB energy in a system containing multiple H-bonds. After explaining and illustrating the methodology of MTA, we present its use for the IHB energy estimation in molecules and clusters. We also discuss the use of this method by other researchers as a standard, state-of-the-art method for estimating IHB energy as well as those of other noncovalent interactions.

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Section: Introductionmentioning

confidence: 99%

“…These have been nicely summarized by Jablonski [ 40 ] in his article in this Special Issue, and we shall discuss only the aspects of these methods (e.g., their merits and demerits) that are not explicitly covered in Ref. [ 40 ].…”

Section: Introductionmentioning

confidence: 99%

Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Deshmukh

Gadre

2021

Molecules

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“…These paths very often correspond to intuitive ideas of chemical bonds. However serious complications are often encountered in the chemical interpretation of bond paths and critical points for weak interactions, as mentioned already [22][23][24][25][26][27][28].…”

Section: Atoms In Moleculesmentioning

confidence: 99%

“…The IUPAC AIM bond path and critical point criteria [12] for the existence of a hydrogen bond is subject to interpretation. Sometimes a path and its critical point seem much at variance with intuitive notions of bonding [22][23][24][25][26]. Bader recognized this awkward conflict, [27] and a proposal that these topological entities be called "line" CPs has been offered.…”

Section: Introductionmentioning

confidence: 99%

Focal Point Evaluation of Energies for Tautomers and Isomers for 3-hydroxy-2-butenamide: Evaluation of Competing Internal Hydrogen Bonds of Types -OH…O=, -OH…N, -NH…O=, and CH…X (X=O and N)

2021

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The title compound is a small molecule with many structural variations; it can illustrate a variety of internal hydrogen bonds, among other noncovalent interactions. Here we examine structures displaying hydrogen bonding between carbonyl oxygen and hydroxyl H; between carbonyl oxygen and amino H; hydroxyl H and amino N; hydroxyl O and amino H. We also consider H-bonding in its tautomer 2-oxopropanamide. By extrapolation algorithms applied to Hartree-Fock and correlation energies as estimated in HF, MP2, and CCSD calculations using the cc-pVNZ correlation-consistent basis sets (N = 2, 3, and 4) we obtain reliable relative energies of the isomeric forms. Assuming that such energy differences may be attributed to the presence of the various types of hydrogen bonding, we attempt to infer relative strengths of types of H-bonding. The Atoms in Molecules theory of Bader and the Local Vibrational Modes analysis of Cremer and Kraka are applied to this task. Hydrogen bonds are ranked by relative strength as measured by local stretching force constants, with the stronger =O…HO- > NH…O= > -OH…N well separated from a cluster > NH…O= ≈ >NH…OH ≈ CH…O= of comparable and intermediate strength. Weaker but still significant interactions are of type CH…N which is stronger than CH…OH.

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“…There are numerous ways to estimate the intramolecular hydrogen bond energy. An extensive survey of various methods that are often used to evaluate the energies of intraHBs has been performed [34]. In the study presented here, the main methods that have been applied are briefly mentioned for comparison with new approaches proposed here.…”

Section: Models To Calculate Energies Of Intramolecular Hydrogen Bondsmentioning

confidence: 99%

Intramolecular Hydrogen Bond Energy and Its Decomposition—O–H∙∙∙O Interactions

Grabowski

2020

Crystals

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The method to calculate the energy of intramolecular hydrogen bond is proposed and tested for a sample of malonaldehyde and its fluorine derivatives; the corresponding calculations were performed at the ωB97XD/aug-cc-pVTZ level. This method based on relationships found for related intermolecular hydrogen bonds is compared with other approaches which may be applied to estimate the intramolecular hydrogen bond energy. Particularly, methods based on the comparison of the system that contains the intramolecular hydrogen bond compared with corresponding conformations where such interaction does not occur are discussed. The function-based energy decomposition analysis, FB-EDA, of the intramolecular hydrogen bonds is also proposed here.

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A Critical Overview of Current Theoretical Methods of Estimating the Energy of Intramolecular Interactions

Cited by 56 publications

References 151 publications

Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Focal Point Evaluation of Energies for Tautomers and Isomers for 3-hydroxy-2-butenamide: Evaluation of Competing Internal Hydrogen Bonds of Types -OH…O=, -OH…N, -NH…O=, and CH…X (X=O and N)

Intramolecular Hydrogen Bond Energy and Its Decomposition—O–H∙∙∙O Interactions

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