Quantum Chemical Investigations on Molecular Clusters

Gadre, Shridhar R.; Yeole, Sachin D.; Sahu, Nityananda

doi:10.1021/cr4006632

Cited by 194 publications

(161 citation statements)

References 802 publications

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“…Figure 4 displays the vibrational spectra of the cationic clusters that is derived after the Hessian and dipole derivative corrections. The calculated spectrum of H 3 19 shows a doublet in the free O-H region, which is very clearly seen on enlargement (figure on the right hand side), in agreement with the experimental findings. [51][52][53] The doublet feature is traced to the presence of two types of free O-H groups, those associated with DAA and DA types of water molecules.…”

Section: Cationic Water Clusterssupporting

confidence: 88%

“…[51][52][53] The doublet feature is traced to the presence of two types of free O-H groups, those associated with DAA and DA types of water molecules. For the former type of free O-H groups, the calculated vibrational spectrum for H 3 19 isomer shows peaks in the range of 3690-3704 cm −1 (with an average value 3699 cm −1 ), in agreement with the experimental results. [51][52][53] In contrast, a sharp peak due to the free O-H vibration associated with the 2-coordinated DA water molecule arises around 3716 cm −1 , also in accordance with previous experimental findings.…”

Section: Cationic Water Clusterssupporting

confidence: 85%

“…Especially, in the case of weakly bonded molecular clusters, the calculated vibrational spectra shed light on the understanding of the atomic contacts/orientations, nucleation phenomena, and extra stability of clusters. 3 Several studies, reporting the theoretically calculated vibrational spectra of a variety of molecular clusters, are available in the literature. [4][5][6][7][8][9][10][11][12][13] Among these, most of the investigations are reported on water clusters.…”

Section: Introductionmentioning

confidence: 99%

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Accurate vibrational spectra via molecular tailoring approach: A case study of water clusters at MP2 level

Sahu

Gadre

2015

The Journal of Chemical Physics

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In spite of the recent advents in parallel algorithms and computer hardware, high-level calculation of vibrational spectra of large molecules is still an uphill task. To overcome this, significant effort has been devoted to the development of new algorithms based on fragmentation methods. The present work provides the details of an efficient and accurate procedure for computing the vibrational spectra of large clusters employing molecular tailoring approach (MTA). The errors in the Hessian matrix elements and dipole derivatives arising due to the approximation nature of MTA are reduced by grafting the corrections from a smaller basis set. The algorithm has been tested out for obtaining vibrational spectra of neutral and charged water clusters at Møller-Plesset second order level of theory, and benchmarking them against the respective full calculation (FC) and/or experimental results. For (H2O)16 clusters, the estimated vibrational frequencies are found to differ by a maximum of 2 cm(-1) with reference to the corresponding FC values. Unlike the FC, the MTA-based calculations including grafting procedure can be performed on a limited hardware, yet take a fraction of the FC time. The present methodology, thus, opens a possibility of the accurate estimation of the vibrational spectra of large molecular systems, which is otherwise impossible or formidable.

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Section: Cationic Water Clusterssupporting

confidence: 88%

Section: Cationic Water Clusterssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

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Accurate vibrational spectra via molecular tailoring approach: A case study of water clusters at MP2 level

Sahu

Gadre

2015

The Journal of Chemical Physics

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“…First of all, we remind the reader that the global minimum reported in the literature for both (H 2 O) 20 and (H 2 O) 24 cluster are cuboidal [19,[48][49][50][51][52][53] in which the insertion sites are too small to accept a guest polyatomic molecule without opening the water network. The (H 2 O) 20 cuboidal structure was confirmed at the MP2 perturbative level of theory [49], while the (H 2 O) 24 24 endohedral complex.…”

Section: Bpl:(h 2 O) 6 Complexmentioning

confidence: 99%

“…A simple, powerful and quick method based on a measurable physical property of molecules and clusters was used to identify favorable interactions between two species: the molecular electrostatic potential (MESP) [2,[19][20][21][22][23][24][25][26][27]. When investigating non-covalent interactions, studies based on the MESP analysis are mainly of two types:  explanatory approach: A quantitative analysis of the isolated monomers MESPs may lead to the identification of electron-rich and electron-deficient regions (σ-holes or π-holes for instance).…”

Section: Introductionmentioning

confidence: 99%

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

2017

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Encapsulation of small (bio-)organic molecules within water cages is governed by a subtle equilibrium between water-water and water-solute interactions. The competition between the formation of exohedral and endohedral complexes is investigated. The first step prior to a theoretical characterization of interactions involved in such complexes lies in the judicious choice of a level of theory. The β-propiolactone (BPL), a solute for which the micro-hydration was recently characterized by means of high resolution microwave spectroscopy (Angew. Chem. 2015, 127, 993), was selected for the present study, and a calibration step is carried out. It is shown that the dispersion-corrected density functional theory (DFT-D) suitably reproduce the geometric, energetic and spectroscopic features of the BPL:(H 2 O) 1-5 complexes. The experimentally-deduced structures of the BPL:(H 2 O) 4,5 species are fully understood in terms of the maximization of interactions between complementary sites in the MESPs. DFT-D calculations followed by the topological analysis within the Quantum Theory of Atoms in Molecules framework have shown that the solute could efficiently interact with (H 2 O) 6,10 clusters in a similar manner that the (H 2 O) 4,5 clusters do. The interaction of the solute with two larger water clusters is further investigated. The exohedral and endohedral BPL:(H 2 O) 20 isomers are close in energy with each other, whereas the formation of an inclusion complex is energetically more favored than the facial interaction in the case of the BPL:(H 2 O) 24 cluster. The topological analysis suggests that the substantial energetic stability is due to interactions between the solute and almost all oxygen atoms of the water cage.

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Irreversible Conversion of a Water–Ethanol Solution into an Organized Two‐Dimensional Network of Alternating Supramolecular Units in a Hydrophobic Zeolite under Pressure

et al. 2017

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Turning disorderi nto organization is ak ey issue in science.B ym aking use of X-rayp owder diffraction and modeling studies,w es how herein that high pressures in combination with the shape and space constraints of the hydrophobic all-silica zeolite ferrierite separate an ethanolwater liquid mixture into ethanol dimer wires and water tetramer squares.T he confined supramolecular blocks alternate in ab inary two-dimensional (2D) architecture that remains stable upon complete pressure release.T hese results support the combined use of high pressures and porous networks as av iable strategy for driving the organization of molecules or nano-objects towards complex, pre-defined patterns relevant for the realization of novel functional nanocomposites.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

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Quantum Chemical Investigations on Molecular Clusters

Cited by 194 publications

References 802 publications

Accurate vibrational spectra via molecular tailoring approach: A case study of water clusters at MP2 level

Accurate vibrational spectra via molecular tailoring approach: A case study of water clusters at MP2 level

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

Irreversible Conversion of a Water–Ethanol Solution into an Organized Two‐Dimensional Network of Alternating Supramolecular Units in a Hydrophobic Zeolite under Pressure

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