Award Abstract # 1855583
RUI: Computational Study of Vibrational Motion in Hydrogen-Bonded Systems

NSF Org: CHE
Division Of Chemistry
Recipient: KENNESAW STATE UNIVERSITY RESEARCH AND SERVICE FOUNDATION, INC
Initial Amendment Date: August 12, 2019
Latest Amendment Date: August 12, 2019
Award Number: 1855583
Award Instrument: Standard Grant
Program Manager: Colby Foss
cfoss@nsf.gov
 (703)292-5327
CHE
 Division Of Chemistry
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: September 1, 2019
End Date: August 31, 2023 (Estimated)
Total Intended Award Amount: $232,892.00
Total Awarded Amount to Date: $232,892.00
Funds Obligated to Date: FY 2019 = $232,892.00
History of Investigator:
  • Martina Kaledin (Principal Investigator)
    mkaledin@kennesaw.edu
Recipient Sponsored Research Office: Kennesaw State University Research and Service Foundation
1000 CHASTAIN RD NW
KENNESAW
GA  US  30144-5588
(470)578-6381
Sponsor Congressional District: 11
Primary Place of Performance: Kennesaw State University
370 Paulding Ave NW
Kennesaw
GA  US  30144-5591
Primary Place of Performance
Congressional District:
11
Unique Entity Identifier (UEI): G8DZHNRKWTN3
Parent UEI:
NSF Program(s): CSD-Chem Strcture and Dynamics
Primary Program Source: 01001920DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 9229, 9263
Program Element Code(s): 910100
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

The Chemical Structure Dynamics and Mechanism (CSDM-A) Program of the Chemistry Division supports Professor Martina Kaledin and her students at Kennesaw State University (KSU) to develop computational methods to study structure and properties of hydrogen-bonded systems. Water (H2O) is an example of a hydrogen bonded system. When hydrogen (H) atoms bond to oxygen (O) atoms, the H atom becomes partly positively charged, and the O atom partly negatively charged. In liquid water, the H2O molecules therefore tend to stick to each other because of the positive-negative attraction between H and O on different H2O molecules. Hydrogen bonding is actually a general feature of many molecules that contain O-H, or N-H (N= nitrogen) bonds as part of their structure. Hydrogen bonding is an important topic of research because it can cause the formation of large networks of molecules and influence the rates and outcome of chemical reactions. The effects of hydrogen bonding are not easy to predict, especially when many atoms and molecules are involved. Professor Kaledin has developed advanced computer models to simulate the behavior and properties of hydrogen bonded systems. She and her students are using high-performance computer systems (IBM HPC computer at KSU) are employed to predict the structure of hydrogen bonded systems as well as their response to light energy. Experimental chemists use what are called spectroscopic techniques to measure how light of different wavelengths (ultraviolet, visible, infrared) are absorbed by molecular systems. Prof. Kaledin is using computational approaches to predict experimental "spectra," which in turn helps experimental scientists understand their observations. The findings of this project are contributing to developing molecular dynamics simulation models which advance our understanding of many chemical systems, as well s complex biological systems. The researchers involved in this project include both undergraduate and graduate students. They are learning principles of supercomputing, molecular modeling, supercomputing, interpretation of vibrational spectra, analyzing the energetics of chemical reactions, and molecular visualization techniques. Prof. Kaledin is also Integrating elements of this research project into her formal undergraduate courses, with the aim to improve science education and STEM students success.

Central to these tasks is to calculate and assign vibrational spectra using driven molecular dynamics (DMD). In the DMD method, an external sinusoidal electric field, representing a continuous wave (CW) laser pulse, is used to scan the spectrum for resonances and obtain an absorption profile. The strength of the external field determines the intensity of the motion. The important feature of DMD is the ability to study the anharmonic motion and mode coupling, and make assignments. At resonant frequencies, the molecular motions induced by weak driven force correspond to the normal-mode frequencies, while harder driving induces anharmonic motion. To identify resonant frequencies, the average internal energy of the molecule is obtained after a finite time of driving. DMD is also easily expandable to two-dimensional spectroscopy, such as 2D-IR, an even more powerful tool for studying complex dynamical structures. These techniques provide detailed dynamic information on protonated water clusters and small molecules relevant to atmospheric chemistry, reveal their stability and timescale of motion of individual groups of atoms. The students involved in this project are being trained in molecular dynamics simulations, ab initio and density functional theory calculation, and interpretation of Raman and infrared spectra (including 2D IR). All of these tools and skills are highly valuable for scientists entering the modern workforce. In addition to advancing other areas of science through the computational models developed in this project, the broader impacts of this work is includes the promotion of strong interactions between the research community and industry, and outreach to students from disadvantaged backgrounds or underrepresented groups, for example through engagement with the Peach State Louis Stokes Alliances for Minority Participation (LSAMP).

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Boutwell, Dalton and Okere, Onyinye and Omodemi, Oluwaseun and Toledo, Alexander and Barrios, Antonio and Olocha, Monique and Kaledin, Martina "Analysis of the Proton Transfer Bands in the Infrared Spectra of Linear N 2 H + ···OC and N 2 D + ···OC Complexes Using Electric Field-Driven Classical Trajectories" The Journal of Physical Chemistry A , v.124 , 2020 https://doi.org/10.1021/acs.jpca.0c06756 Citation Details
Boutwell, Dalton and Pierre-Jacques, Dominick and Cochran, Olivia and Dyke, Jason and Salazar, Dayana and Tyler, Ciara and Kaledin, Martina "Intramolecular Proton Transfer in the Hydrogen Oxalate Anion and the Cooperativity Effects of the Low-Frequency Vibrations: A Driven Molecular Dynamics Study" The Journal of Physical Chemistry A , v.126 , 2022 https://doi.org/10.1021/acs.jpca.1c09686 Citation Details
Hashem, Younos and Foust, Katheryn and Kaledin, Martina and Kaledin, Alexey L. "Fitting Potential Energy Surfaces by Learning the Charge Density Matrix with Permutationally Invariant Polynomials" Journal of Chemical Theory and Computation , v.19 , 2023 https://doi.org/10.1021/acs.jctc.3c00586 Citation Details
Kudratov, Sophia A. and Kaledin, Martina and Kaledin, Alexey L. "Revisiting the N ( N +1)/2site s type Gaussian charge model for permutationally invariant polynomial fitting of global molecular tensor surfaces" International Journal of Quantum Chemistry , v.123 , 2023 https://doi.org/10.1002/qua.27102 Citation Details
Omodemi, Oluwaseun and Kaledin, Martina and Kaledin, Alexey L. "Permutationally invariant polynomial representation of polarizability tensor surfaces for linear regression analysis" Journal of Computational Chemistry , v.43 , 2022 https://doi.org/10.1002/jcc.26952 Citation Details
Omodemi, Oluwaseun and Revennaugh, Ramsay and Riley, Janiyah and Kaledin, Alexey L. and Kaledin, Martina "A Fermi resonance and a parallel-proton-transfer overtone in the Raman spectrum of linear centrosymmetric N4H+: A polarizability-driven first principles molecular dynamics study" The Journal of Chemical Physics , v.157 , 2022 https://doi.org/10.1063/5.0119251 Citation Details
Omodemi, Oluwaseun and Sprouse, Sarah and Herbert, Destyni and Kaledin, Martina and Kaledin, Alexey L. "On the Cartesian Representation of the Molecular Polarizability Tensor Surface by Polynomial Fitting to Ab Initio Data" Journal of Chemical Theory and Computation , v.18 , 2022 https://doi.org/10.1021/acs.jctc.1c01015 Citation Details
Pierre-Jacques, Dominick and Tyler, Ciara and Dyke, Jason and Kaledin, Alexey L. and Kaledin, Martina "A polarizability driven ab initio molecular dynamics approach to stimulating Raman activity: Application to C 20" Molecular Physics , 2021 https://doi.org/10.1080/00268976.2021.1939453 Citation Details

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

This RUI award facilitated the research activities of P.I. Kaledin and her students at Kennesaw State University. Their work focused on proton transfer in hydrogen-bonded complexes.  They have developed and applied various computational methods, such as normal mode analysis, direct molecular dynamics (MD), and driven MD (DMD) to obtain and assign infrared and Raman spectra of hydrogen-bonded systems, such as protonated water cluster H5O2+, hydrogen oxalate anion [C2O4H]-, formic acid dimer, (HCOOH)2, protonated nitrogen dimer, N4H+, and its isoelectronic analog N2H+OC. Also, they have studied the vibrational spectra of other molecules, CH4, CCl4, CHCl3, formamide, and a much larger molecule, fullerene, C20 to test the accuracy and feasibility of the newly developed methods and address symmetry aspects of molecular vibrations. 

In this work, Raman spectra of H5O2+ and N4H+ and their isotopic analogs in the complete spectral range of  0-4000 cm-1 were presented for the very first time using first principles potential energy and polarizability surfaces. Elements of 2D pump-probe Raman spectroscopy helped to identify Fermi resonance between the symmetric N-N stretch fundamental and the overtone corresponding to perpendicular N⋯H+⋯N proton transfer in the protonated nitrogen dimer, N4H+ spectrum.  Additionally, computer simulations resolved overlapping peaks in the low-frequency range of the protonated water dimer, H5O2+ near the O-O stretch fundamental that is IR dark. The simulations of the oxalate anion showed that the low-frequency bending modes played a crucial role in the proton transfer motion that occurs on a non-linear path. These model systems provide insights into our understanding of proton transfer that are relevant to acid-base chemistry, astrochemistry, and material science.

The Driven Molecular Dynamics (DMD) method developed by P.I. Kaledin continues to evolve as a valuable tool for mode assignments in IR and Raman spectra. Innovative data analysis techniques helped visualize the atomic motion at resonances that correspond to anharmonic spectral activities, providing key information on mode coupling and vibrational energy transfer. Fitting of multidimensional potential energy (PES), dipole moment (DMS), and polarizability tensor (PTS) surfaces to high-level ab initio electronic structure data along with basic elements of machine learning, such as linear regression analysis has a great potential to improve the computational efficiency of simulation techniques.

This award contributed to strengthening undergraduate programs (B. S. in Chemistry, B.S. in Biochemistry) and M. S. program in Chemical Sciences at Kennesaw State University. It enabled the purchase of the MOLPRO program, the software that was used in our research project, and the training of students. The research projects that were developed during the project have enriched curricular activities in various courses in the form of computational exercises for both undergraduate and graduate students. Students gained a solid foundation in computational chemistry methods and made connections to physical chemistry topics such as quantum chemistry, molecular symmetry, and atomic and molecular spectroscopy. Such a research experience made a positive impact on the retention of students in STEM. Also, research projects enriched curricular activities in the Physical Chemistry undergraduate courses, Honor Capstone projects, Directed Applied Research, Physical and Analytical Methods graduate course, and Research for Master Thesis. The P.I. Kaledin also emphasized research ethics and discussed topics of responsible conduct in research. Students conducted literature research, learned the Linux operating system, wrote codes, ran computer simulations, and worked on improving their presentation skills by attending scientific meetings. Two graduate students and 19 undergraduate students co-authored papers. Of those students, 56 % were female, and 60 % underrepresented students who were recruited from the classroom and from the LSAMP program (Louis Stokes Alliance for Minority participation). P.I. and students also participated in recruitment activities at local high schools, ACS, and SERMACS meetings. 

Expanded computational resources allowed the principal investigator to establish new collaborations with investigators at other research institutions (Emory University, Atlanta, GA) and helped to recruit research-active faculty. Multiple students advanced their academic careers to graduate schools, completed MS and Ph.D. programs, and entered the workforce in STEM-related disciplines. 



Last Modified: 11/15/2023
Modified by: Martina Kaledin

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