Hydration shell model for expeditious and reliable individual hydrogen bond energies in large water clusters

Ahirwar, Mini Bharati; Gurav, Nalini D.; Gadre, Shridhar R.; Deshmukh, Milind M.

doi:10.1039/d2cp01663j

Cited by 12 publications

(38 citation statements)

References 72 publications

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“…These O−H…O HB energies are found to be in the range 3.97 to 10.30 kcal mol −1 . These calculated O−H…O HB energies in (NH 3 ) m (H 2 O) n (n+m=2 to 7) clusters are seen to be similar of strengths to those in water clusters, studied in our earlier work [70,71] . Tables 1 and 2 reveal that the individual O−H…N HBs are moderately stronger than the O−H…O HBs.…”

Section: Resultssupporting

confidence: 69%

“…These calculated OÀ H…O HB energies in (NH 3 ) m (H 2 O) n (n + m = 2 to 7) clusters are seen to be similar of strengths to those in water clusters, studied in our earlier work. [70,71] Tables 1 and 2 reveal that the individual OÀ H…N HBs are moderately stronger than the OÀ H…O HBs. The OÀ H…O HB energies in dimers also seen to be moderately smaller (3.85 to 5.23 kcal mol À 1 ) than the respective OÀ H…N HB energies counterparts.…”

Section: The Oà H…o Hb Energy and Cooperativity In Neutral (Nh 3 ) M ...mentioning

confidence: 99%

“…A closer look at these HBs (HB2 and HB4) suggests that they are involved in the formation of anti-cooperative network of HBs, wherein, the direction of these two HBs are opposite to each other. It has been suggested in the literature that the formation of such anti-cooperative network of HBs, results in the smaller or negative cooperativity contributions [70,71] (À 0.64 and À 0.32 kcal mol À 1 , respectively). For this reason, the energy of these HBs is smaller (See Table 1).…”

Section: Chemphyschemmentioning

confidence: 99%

“…This structural feature is denoted as AA(W D )!W A (DD) and was attributed to the formation of strong HBs in water clusters, studied in our earlier work. [70,71,76] Furthermore, it has been suggested that the strong HBs have large contribution of cooperativity. Indeed, the cooperativity ChemPhysChem contribution towards HB3 in (NH 3 ) 1 (H 2 O) 6 is the largest (6.10 kcal mol À 1 ) among all the other OÀ H…O HBs.…”

Section: The Oà H…o Hb Energy and Cooperativity In Neutral (Nh 3 ) M ...mentioning

confidence: 99%

“…[63][64][65][66][67][68][69] This methodology was successfully extended by Deshmukh and co-workers, for estimating the individual HB energy and cooperativity in various molecular clusters viz. water (H 2 O) n , [70,71] ammonia (NH 3 ) n , [72] hydrogen fluoride (HF) n , [73] benzene (Bz) n , [74] and mixed (HF) m -(H 2 O) n [75] as well as methanol-water (CH 3 OH) m (H 2 O) n [76] clusters. The calculated HB energies in (H 2 O) n , (n = 3 to 8) clusters, lie in the wide range of 0.3 to 11.6 kcal mol À 1 at MP2/aug-cc-pVTZ level.…”

Section: Introductionmentioning

confidence: 99%

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A Tug of War between the Self‐ and Cross‐associating Hydrogen Bonds in Neutral Ammonia‐Water Clusters: Energetic Insights by Molecular Tailoring Approach

2022

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In the present work, the energies of various types of individual HBs observed in neutral (NH3)m(H2O)n, (m+n=2 to 7) clusters were estimated using the molecular tailoring approach (MTA)‐based method. The calculated individual HB energies suggest that the O−H…N HBs are the strongest (1.21 to 12.49 kcal mol−1). The next ones are the O−H…O (3.97 to 9.30 kcal mol−1) HBs. The strengths of N−H…N (1.09 to 5.29 kcal mol−1) and N−H…O (2.85 to 5.56 kcal mol−1) HBs are the weakest. The HB energies in dimers also follow this rank ordering. However, the HB energies in dimers are much smaller than those obtained by the MTA‐based method due to the loss in cooperativity contribution in the dimers. Thus, the calculated cooperativity contributions, for different types of HBs, fall in the range 0.64 to 5.73 kcal mol−1. We wish to emphasize based on the energetic rank ordering obtained by the MTA‐based method that the O−H of water is a better HB donor than the N−H of ammonia. The reasons for the observed energetic rank ordering are two folds: (i) intrinsically stronger O−H…N HBs than the O−H…O ones as revealed by dimer energies and (ii) the higher cooperativity contribution in the former than the later ones. Indeed, the MTA‐based method is useful in providing the missing energetic rank ordering of various type of HBs in neutral (NH3)m(H2O)n clusters, in the literature.

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Section: Resultssupporting

confidence: 69%

Section: The Oà H…o Hb Energy and Cooperativity In Neutral (Nh 3 ) M ...mentioning

confidence: 99%

Section: Chemphyschemmentioning

confidence: 99%

Section: The Oà H…o Hb Energy and Cooperativity In Neutral (Nh 3 ) M ...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A Tug of War between the Self‐ and Cross‐associating Hydrogen Bonds in Neutral Ammonia‐Water Clusters: Energetic Insights by Molecular Tailoring Approach

2022

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Fragments‐in‐fragments method for efficient and reliable estimates of individual hydrogen bond energies in large molecular clusters

Ahirwar

Deshmukh

2023

J Comput Chem

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The knowledge of individual hydrogen bond (HB) strength in molecular clusters is indispensable to get insights into the bulk properties of condensed systems. Recently, we have developed the molecular tailoring approach based (MTA-based) method for the estimation of individual HB energy in molecular clusters. However, the direct use of this MTA-based method to large molecular clusters becomes progressively difficult with the increase in the size of a cluster. To overcome this caveat, herein, we propose the use of linear scaling method (such as the original MTA method) for the estimation of single-point (SP) energies of large-sized parent molecular cluster and their respective fragments. Because the fragments of the MTA-based method, for the estimation of HB energy, are further fragmented, this proposed strategy is called as Fragments-in-Fragments (Frags-in-Frags) method. The SP energies of fragments and parent cluster calculated by the Frags-in-Frags approach were utilized to estimate the individual HB energy. The estimated individual HB energies, in various molecular clusters, by Fragsin-Frags method are found to be in excellent linear agreement with their MTA-based counterparts (R 2 = 0.9975 of 348 data points). The difference being less than 0.5 kcal/ mol in most of the cases. Furthermore, RMSD is 0.43 kcal/mol, MAE is 0.33 kcal/mol, and the standard deviation is 0.44 kcal/mol. Importantly, the Frags-in-Frags method not only enables the reliable estimation of HB energy in large molecular clusters but also requires less computational time and can be possible even with off-the-shelf hardware.

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Hydrogen bond energy estimation (H‐BEE) in large molecular clusters: A Python program for quantum chemical investigations

Ahirwar,

Khire,

Gadre

et al. 2023

J Comput Chem

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A procedure, derived from the fragmentation‐based molecular tailoring approach (MTA), has been proposed and extensively applied by Deshmukh and Gadre for directly estimating the individual hydrogen bond (HB) energies and cooperativity contributions in molecular clusters. However, the manual fragmentation and high computational cost of correlated quantum chemical methods make the application of this method to large molecular clusters quite formidable. In this article, we report an in‐house developed software for automated hydrogen bond energy estimation (H‐BEE) in large molecular clusters. This user‐friendly software is essentially written in Python and executed on a Linux platform with the Gaussian package at the backend. Two approximations to the MTA‐based procedure, viz. the first spherical shell (SS1) and the Fragments‐in‐Fragments (Frags‐in‐Frags), enabling cost‐effective, automated evaluation of HB energies and cooperativity contributions, are also implemented in this software. The software has been extensively tested on a variety of molecular clusters and is expected to be of immense use, especially in conjunction with correlated methods such as MP2, CCSD(T), and so forth.

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Hydration shell model for expeditious and reliable individual hydrogen bond energies in large water clusters

Abstract: Recently, we have developed and tested a method, based on the molecular tailoring approach (MTA-based) to directly estimate the individual hydrogen bond (HB) energies in molecular clusters. Application of this...

Cited by 12 publications

References 72 publications

A Tug of War between the Self‐ and Cross‐associating Hydrogen Bonds in Neutral Ammonia‐Water Clusters: Energetic Insights by Molecular Tailoring Approach

A Tug of War between the Self‐ and Cross‐associating Hydrogen Bonds in Neutral Ammonia‐Water Clusters: Energetic Insights by Molecular Tailoring Approach

Fragments‐in‐fragments method for efficient and reliable estimates of individual hydrogen bond energies in large molecular clusters

Hydrogen bond energy estimation (H‐BEE) in large molecular clusters: A Python program for quantum chemical investigations

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