Electronic Effects in Organic Chemistry

Liquid organic hydrogen carriers (LOHC) are an interesting and promising option for the storage and transport of hydrogen with reasonable energy density via a reversible hydrogenation reaction. The commercially available heat transfer oil dibenzyltoluene emerged as a potential carrier for the LOHC technology due to its availability, thermal stability, and reasonable hydrogen storage capacity. In this work, thermophysical property data (viscosity, density, surface tension, and refractive index) are measured for dibenzyltoluene and its partially and fully hydrogenated derivatives, namely, hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene, and octadecahydro-dibenzyltoluene over a wide range of temperatures. Correlations for the temperature dependence are proposed for the measured properties. Moreover, the excess molar volume is reported within the temperature range from 293.15 K to 358.15 K for the binary mixtures of dibenzyltoluene (fully dehydrogenated form) and octadecahydro-dibenzyltoluene (fully hydrogenated form). Positive values for the excess molar volumes are observed over the entire concentration range.

show abstract

DFT-based QM/MM with particle-mesh Ewald for direct, long-range electrostatic embedding

Pederson

McDaniel

2022

The Journal of Chemical Physics

View full text Add to dashboard Cite

We present a DFT-based, QM/MM implementation with long-range electrostatic embedding achieved by direct real-space integration of the particle mesh Ewald (PME) computed electrostatic potential. The key transformation is the interpolation of the electrostatic potential from the PME grid to the DFT quadrature grid, from which integrals are easily evaluated utilizing standard DFT machinery. We provide benchmarks of the numerical accuracy with choice of grid size and real-space corrections, and demonstrate that good convergence is achieved while introducing nominal computational overhead. Furthermore, the approach requires only small modification to existing software packages, as is demonstrated with our implementation in the OpenMM and Psi4 software. After presenting convergence benchmarks, we evaluate the importance of long-range electrostatic embedding in three solute/solvent systems modeled with QM/MM. Water and BMIM/BF4 ionic liquid were considered as ``simple' and ``complex' solvents respectively, with water and p-phenylenediamine (PPD) solute molecules treated at QM level of theory. While electrostatic embedding with standard real-space truncation may introduce negligible error for simple systems such as water solute in water solvent, errors become more significant when QM/MM is applied to complex solvents such as ionic liquids. An extreme example is the electrostatic embedding energy for oxidized PPD in BMIM/BF4 for which real-space truncation produces severe error even at 2-3 nm cutoff distances. This latter example illustrates that utilization of QM/MM to compute redox potentials within concentrated electrolytes/ionic media requires carefully chosen long-range electrostatic embedding algorithms, with our presented algorithm providing a general and robust approach.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Electronic Effects in Organic Chemistry

Cited by 5 publications

References 163 publications

Amino-coumarin-based colorimetric and fluorescent chemosensors capable of discriminating Co2+, Ni2+, and Cu2+ ions in solution and potential utilization as a paper-based device

Amino-coumarin-based colorimetric and fluorescent chemosensors capable of discriminating Co2+, Ni2+, and Cu2+ ions in solution and potential utilization as a paper-based device

Thermophysical Studies of Dibenzyltoluene and Its Partially and Fully Hydrogenated Derivatives

DFT-based QM/MM with particle-mesh Ewald for direct, long-range electrostatic embedding

Contact Info

Product

Resources

About