Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Deshmukh, Milind M.; Gadre, Shridhar R.

doi:10.3390/molecules26102928

Cited by 37 publications

(25 citation statements)

References 116 publications

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“…In the previous decade, Gadre and Deshmukh developed a fragmentation-based method for the estimation of individual intramolecular HB energy (IHBE) in a variety of systems. [32][33][34][35][36][37][38] This methodology was successfully extended by Deshmukh and co-workers, for estimating the individual HB energy and cooperativity in various molecular clusters viz. water (W n ), [39] ammonia (NH 3 ) n , [40] hydrogen fluoride (HF) n [41] and mixed (HF) m -(W) n [42] clusters.…”

Section: Introductionmentioning

confidence: 99%

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

2022

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In this work, we examine the strength of various types of individual hydrogen bond (HB) in mixed methanol-water M n W m , (n + m = 2 to 7) clusters, with an aim to understand the relative order of their strength, using our recently proposed molecular tailoring-based approach (MTA). Among all the types of HB, it is observed that the O M À H…O W HBs are the strongest (6.9 to 12.4 kcal mol À 1 ). The next ones are O M À H…O M HBs (6.5 to 11.6 kcal mol À 1 ). The O W À H…O W (0.2 to 10.9 kcal mol À 1 ) and O W À H…O M HBs (0.3 to 10.3 kcal mol À 1 ) are the weakest ones. This energetic ordering of HBs is seen to be different from the respective HB energies in the dimer i. e., O M À H…O M (5.0 to 6.0 kcal mol À 1 ) > O W À H…O M (1.5 to 6.0 kcal mol À 1 ) > O M À H…O W (3.8 to 5.6 kcal mol À 1 ) > O W À H…O W (1.2 to 5.0 kcal mol À 1 ). The plausible reason for the difference in the HB energy ordering may be attributed to the increase or decrease in HB strengths due to the formation of cooperative or anti-cooperative HB networks. For instance, the cooperativity contribution towards the different types of HB follows: O M À H…O W (2.4 to 8.6 kcal mol À 1 ) > O M À H…O M (1.3 to 6.3 kcal mol À 1 ) > O W À H…O W (À 1.0 to 6.5 kcal mol À 1 ) > O W À H…O M (À 1.2 to 5.3 kcal mol À 1 ). This ordering of cooperativity contribution is similar to the HB energy ordering obtained by the MTA-based method. It is emphasized here that, the interplay between the cooperative and anti-cooperative contributions are indispensable for the correct energetic ordering of these HBs.

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Section: Introductionmentioning

confidence: 99%

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

2022

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“…In the recent past, a fragmentation-based method for the estimation of individual intramolecular hydrogen-bond energy (IHBE) in a variety of systems was proposed by Deshmukh and Gadre. − This methodology has been extended for estimating the individual HB energy and cooperativity in water (W n ) and ammonia clusters (NH 3 ) n and also for the energies of individual intermolecular interactions in benzene (Bz) n clusters. With the aim of exploring the strong associative interconnected network of HBs in HF clusters, in this work, we study some linear (L) and cyclic (C) hydrogen fluoride (HF) n clusters employing our molecular tailoring approach (MTA)-based method. − …”

Section: Introductionmentioning

confidence: 99%

Unusually Large Hydrogen-Bond Cooperativity in Hydrogen Fluoride Clusters, (HF)_n,n= 3 to 8, Revealed by the Molecular Tailoring Approach

et al. 2021

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In this work, our recently proposed molecular tailoring approach (MTA)-based method is employed for the evaluation of individual hydrogen-bond (HB) energies in linear (L) and cyclic (C) hydrogen fluoride clusters, (HF) n (n = 3 to 8). The estimated individual HB energies calculated at the MP2(full)/aug-cc-pVTZ level for the L-(HF) n are between 6.2 to 9.5 kcal/mol and those in the C-(HF) n lie between 7.9 to 11.4 kcal/mol. The zero-point energy corrections and basis set superposition corrections are found to be very small (less than 0.6 and 1.2 kcal/mol, respectively). The cooperativity contribution toward individual HBs is seen to fall between 1.0 to 4.8 kcal/mol and 3.2 to 6.9 kcal/mol for linear and cyclic clusters, respectively. Interestingly, the HB energies in dimers, cleaved from these clusters, lie in a narrow range (4.4 to 5.2 kcal/mol) suggesting that the large HB strength in (HF) n clusters is mainly due to the large cooperativity contribution, especially for n ≥ 5 (50 to 62% of the HBs energy). Furthermore, the HB energies in these clusters show a good qualitative correlation with geometrical parameters (H···F distance and F–H···F angles), stretching frequencies of F–H bonds, and electron density values at the (3, −1) bond critical points.

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“…In the recent past, we have developed a fragmentation-based method for the estimation of individual intramolecular hydrogen bond energy (IHBE) in a variety of systems. − This method not only provides the individual IHBE but also gives the contribution of cooperativity due to inter-connected networking of such intramolecular hydrogen bonds. − Recently, we have extended this methodology for estimating the individual hydrogen bond (H-bond) energies and cooperativity in water (W) clusters . The calculated H-bond energies in W n , for n = 3–8, lie in the wide range of 0.3–10.7 kcal/mol at the CCSD(T)/aug-cc-pVDZ level.…”

Section: Introductionmentioning

confidence: 99%

Molecular Tailoring Approach for Estimating Individual Intermolecular Interaction Energies in Benzene Clusters

et al. 2021

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There is no general method available for the estimation of individual intermolecular interaction energies in weakly bound molecular clusters, and such studies are limited only to the dimer. Recently, we proposed a molecular tailoring approach-based method for the estimation of individual O–H···O hydrogen bond energies in water clusters. In the present work, we extend the applicability of this method for estimating the individual intermolecular interaction energies in benzene clusters, which are expected to be small. The basis set superposition error (BSSE)-corrected individual intermolecular interaction energies in linear (LN) benzene clusters, LN-(Bz) n n = 3–7, were calculated to be in the range from −1.75 to −2.33 kcal/mol with the cooperativity contribution falling between 0.05 and 0.20 kcal/mol, calculated at the MP2.5/aug-cc-pVDZ level of theory. In the case of non-linear (NLN) benzene clusters, NLN-(Bz) n n = 3–5, the BSSE-corrected individual intermolecular interaction energies exhibit a wider range from −1.16 to −2.55 kcal/mol with cooperativity contribution in the range from 0.02 to −0.61 kcal/mol. The accuracy of these estimated values was validated by adding the sum of interaction energies to the sum of monomer energies. These estimated molecular energies of clusters were compared with their actual calculated values. The small difference (<0.3 kcal/mol) in these two values suggests that our estimated individual intermolecular interaction energies in benzene clusters are quite reliable.

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Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Cited by 37 publications

References 116 publications

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

Unusually Large Hydrogen-Bond Cooperativity in Hydrogen Fluoride Clusters, (HF)_n,n= 3 to 8, Revealed by the Molecular Tailoring Approach

Molecular Tailoring Approach for Estimating Individual Intermolecular Interaction Energies in Benzene Clusters

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Molecular Tailoring Approach for the Estimation of Intramolecular Hydrogen Bond Energy

Cited by 37 publications

References 116 publications

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

Energetic Ordering of Hydrogen Bond Strengths in Methanol‐Water Clusters: Insights via Molecular Tailoring Approach

Unusually Large Hydrogen-Bond Cooperativity in Hydrogen Fluoride Clusters, (HF)n,n= 3 to 8, Revealed by the Molecular Tailoring Approach

Molecular Tailoring Approach for Estimating Individual Intermolecular Interaction Energies in Benzene Clusters

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Unusually Large Hydrogen-Bond Cooperativity in Hydrogen Fluoride Clusters, (HF)_n,n= 3 to 8, Revealed by the Molecular Tailoring Approach