Research Activities

IV. Modeling greenhouse gas capture:

Carbon dioxide (CO2) is one of the major greenhouse gas attributing to the global climate changes. The most popular technology used to remove the CO2 from large emission sources is to employ amine based solvents. However, these amine based solvents are highly volatile, liable to be corrosive and consumes a significant amount of energy for solvent regeneration. Therefore, potential substitutes which are environment friendly and cost efficient are of vital importance. Ionic Liquids appear as one of them because of their low volatility, good thermal stability, negligible vapour pressure, and inflamability. The enormous amount of potential ILs increase the challenge to search the best candidate for CO2 solubility. We introduces a thermodynamic model for asymmetric solutions with a special emphasis on solute–solvent interactions and called it "LANL" activity coefficient (ac.) model which is based on a new solvation model based on the asymmetric interaction between solute-solvent molecule. When the COSMOSAC model will be augmented into the "LANL" ac. model,  it will be called as “COSMOSAC-LANL” ac. model. The new “COSMOSAC-LANL” activity coefficient model has been used to calculate the solubility of CO2 in room temperature ionic liquids and to model the selectivity between CO2 and CH4 gases. We have shown improved solubility and selectivity prediction of CO2 and CH4 gas in room temperature ionic liquids using the ADF-COSMOSAC-2013 model with the new “LANL” activity coefficient model.                                                                                                                                                         

Relevant publications:

1. Modeling solubility of CO2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: A first principles study; Anwesa Karmakar* & Rangachary Mukundan [Published: Physical Chemistry Chemical Physics, 21 (2019) 19667-19685  paper & SI]

2.  P525977 Greenhouse Gas Capture : A Recent Theoretical Advancement;

Authors: Anwesa Karmakar*, Enrique R. Batista & Ping Yang  in " 2018 AIChE Annual Meeting" at Pittsburgh, USA. 

[AIChE Conference Proceedings "Recent Advances in Molecular Simulation Methods II" paper (conference link)]; ISBN: 978-0-8169-1108-0

Funding: Laboratory Directed Research and Development Program, USA , Department of Energy USA  

III. A theory guided approach towards the development of highly efficient redox flow cell

Flow batteries are highly popular as storage device and can store large amount of charges in stationary applications. High efficiency flow cells have become an important option to store electric energy on grid scale. The efficiency of flow battery depends on the energy density  which is directly depends on the solubility of ions in the aqueous electrolyte like vanadium redox flow cell. Disadvantages: (a) The use of aqueous electrolyte solutions makes this flow battery unnecessarily heavy, (b) This battery has relatively poor energy to volume ratio also. One can increase the efficiency of a flow cell by increasing the energy density without affecting the power density by directly increasing the solubility of redox active species in non-aqueous electrolyte. Proposed approach: Developing a first principle theoretical predictive model to screen charge carrier complexes with high solubility in non-aqueous electrolytes mainly in ionic liquids or in the mixture of ionic liquid and organic solvents (e.g. Acetonitrile) which will promote the creation of more dense energy system for developing  new highly efficient flow cell.      

Relevant publications:

1. Solubility Model of Metal Complex in Ionic Liquids from First Principle Calculations; Anwesa Karmakar*, Rangachary Mukundan, Ping Yang & Enrique R. Batista [Published: RSC Advances, 2019 paper & SI]

2. Modeling Solubility of Few Tris Acetylacetonato (acac) Transition Metal Complexes and Their Derivatives in Certain Ionic Liquids from First Principle Molecular Simulation: Application to Redox Flow Cell; Anwesa Karmakar*, Rangachary Mukundan, Ping Yang & Enrique R. Batista; [CNLS Conference: Workshop on Non-Aqueous Flow Batteries; poster]

3. Modeling solubility of Metal Complexes in Non-Aqueous Media from First Principle Calculations: Application to Redox Flow Cell; Anwesa Karmakar*, Ping Yang & Enrique R. Batista in " 2018 AIChE Annual Meeting" at Pittsburgh, USA. 

[AIChE Conference Proceedings "Industrial Application of Computational Chemistry and Molecular Simulation" paper (conference link)]; ISBN: 978-0-8169-1108-0

4.  Screening of metal complexes and organic solvents using COSMOSAC-LANL model to enhance the energy density in non-aqueous redox flow cell: an insight into the solubility; Anwesa Karmakar*, Rangachary Mukundan, Ping Yang & Enrique R. Batista [Published: Physical Chemistry Chemical Physics, 2021 paper , SI1 & SI2]

Funding: Laboratory Directed Research and Development Program, USA, Department of Energy USA

II. Development of a mesoscopic model for liquid-liquid solvent extraction 

Solvent extraction plays a very important role in the field of nuclear industry to reprocess the nuclear fuel. The separation technique is the basic principle behind liquid-liquid solvent extraction procedure where an aqueous electrolyte solution comes in contact with an ampiphilic extractant in the organic phase to be selectively extracted from the aqueous phase. All these chemical species are in equilibrium with each other during extraction procedure. From the previous studies, it has been found that such type of solvent extraction process involves the formation of inverse micelle of certain aggregation number of N free extractant monomers. The extraction properties is found to be influenced by the formation of the reverse micelle in the organic phase. The packing parameter of micelle plays a very significant role during the transfer of solute from the aqueous phase to the organic phase affecting the curvature of the micelle. From the study of Leodidis and Hatton, it is known that the free energy of transfer varies within the curvature of the interfacial film monotonically.                                                                                                                                                                      

Relevant Publications:

1. Combined Supramolecular and Mesoscale Modelling of Liquid-Liquid Extraction of Rare Earth Salts; Anwesa Karmakar, Magali Duvail, Michael Bley, Thomas Zemb & Jean-François Dufrêche [Published: Colloids and Surfaces A: Physicochemical and Engineering Aspects (2018) paper]

2. Micelle model for liquid-liquid solvent extraction; Anwesa Karmakar, Magali Duvail, Jean-Francois Dufreche & Thomas Zemb; COST MP1106: smart and green interfaces 

3. A predictive model of reverse micelles solubilizing water for solvent extraction; Michael Bley, Bertrand Siboulet, Anwesa Karmakar, Thomas Zemb & Jean-Francois Dufreche [Published: Journal of Colloid & Interface Science, 479 (2016) 106-114 paper]

4. [Conference paper] P537926 Mesoscale Modeling of Liquid-Liquid Solvent Extraction from Soft Matter Approach; Anwesa Karmakar, Magali Duvail, Michael Bley, Thomas Zemb & Jean-Francois Dufreche in " 2018 AIChE Annual Meeting" at Pittsburgh, USA. [AIChE Conference Proceedings "Molecular simulation and modeling of complex molecules" paper (conference link)]; ISBN: 978-0-8169-1108-0

Funding: European Research Council (ERC-Advanced grant)                                                                                                                                                         

I. Hydrogen bonded structural and dynamical properties of aqueous solutions

In presence of ions, water molecules can form two types of hydrogen bonds: one with the negatively charged ions and other with the nearest water molecules. The presence of ions can influence the local structure of water inside the solvation shell of ions. When ions are present in water, they can behave like either ‘structure breaker’ or ‘structure maker’ entities depending on whether the ions break the hydrogen bonded structure or strengthen it. The study of hydrogen bond dynamics of water molecule in presence of ion has been getting importance in recent years because it has been found that biological macromolecules like  proteins may go through salt out or salt in effects in presence of ions in aqueous medium.  The order of ions based on the protein folding ability is known as Hofmeister series effect .  It has been experimentally found that the Hofmeister series effect is determined primarily by two factors: hydrogen bond interaction and dispersion forces. Clearly, studies of these effects in aqueous medium are of vital importance in solution chemistry.

My main research area covers the study of dynamical behavior of aqueous ionic solution and flexible solute in aqueous systems through ab initio molecular dynamics. The dynamics has been investigated through frequency fluctutations of specific vibational modes of the solutes and the  fluctuation dynamics of such modes are linked to the fluctuations in surrounding environment , by using computer simulation. Ab initio molecular dynamics simulations have been carried out for aqueous fluoride, bromide, iodide and azide ion solutions at two different concentrations at  ambient condition and for the liquid water at (I) ambient and (II) supercritical conditions by using   Car-Parinello and Born-Oppenheimer molecular dynamics simulations in few cases.The effect of dispersion interaction on the dynamics of vibrational spectral diffusion has been looked at  thoroughly.                                                                                                                                                                     

Relevant Publicationss: 

1. Structure, Dynamics and Spectral Diffusion of Water from First Principles Molecular Dynamics; Arindam Bankura, Anwesa Karmakar, Vincenzo Carnevale, Amalendu Chandra & Michael L. Klein [ Published : Journal of Physical Chemistry C 118 (2014) 29401-29411 paper ]

2. Effects of Dispersion Interaction on Vibrational Spectral Diffusion in Aqueous NaBr Solutions: An Ab Initio Molecular Dynamics Study; Anwesa Karmakar & Amalendu Chandra [Published : Chemical Physics, 448 (2015) 1-8 paper]

3. Ab Initio Molecular Dynamics Studies of Hydrogen Bonded Structure, Molecular Motion and Frequency Fluctuations of Water in The Vicinity of Azide Ions; Anwesa Karmakar & Amalendu Chandra [Published : Journal of Chemical Physics, 142 (2015) 164505-10 paper]

4. Water in Hydration Shell of an Iodide Ion: Structure and Dynamics of Solute-water Hydrogen Bonds and Vibrational Spectral Diffusion from First Principles Simulations; Anwesa Karmakar & Amalendu Chandra [Published : Journal of Physical Chemistry B, 2015, 119 (27), 8561-8572 paper]

Funding: Department of Science and Technology, India