Condensed Phase and Interfacial Molecular Science

The CPIMS program accepts and reviews proposals continuously under the annual FOA entitled, “Continuation of Solicitation for the Office of Science Financial Assistance Program”. However, it is preferred that proposals are received by December 04, 2017 to guarantee consideration for funding within fiscal year 2018. Preproposals or white papers are strongly encouraged for all new proposals and should be submitted well in advance of December 04. Please contact the program manager prior to submission. 

The CPIMS program emphasizes basic research at the boundary of chemistry and physics, pursuing a molecular-level understanding of chemical, physical, and electron- and photon-driven processes in liquids and at interfaces. With its foundation in chemical physics, the impact of this crosscutting program on DOE missions is far reaching, including energy utilization, catalytic and separation processes, chemical synthesis, energy storage, and subsurface chemical and transport processes. Experimental and theoretical investigations in the condensed phase and at interfaces aim at elucidating the molecular-scale chemical and physical properties and interactions that govern chemical reactivity, solute/solvent structure and transport.  Studies of reaction dynamics at well-characterized surfaces and clusters lead to the development of theories on the molecular origins of surface-mediated catalysis and heterogeneous chemistry. Studies of model condensed-phase systems target first-principles understanding of molecular reactivity and dynamical processes in solution and at interfaces, including complex interfaces. Fundamental studies of reactive processes driven by radiolysis in condensed phases and at interfaces provide improved understanding of radiation-driven chemistry in nuclear fuel and waste environments.

Basic research is also supported to develop new experimental and theoretical tools that push the horizon of spatial and temporal resolution needed to probe chemical behavior selectively at interfaces and in solution, enabling studies of composition, structure, bonding and reactivity at the molecular level. The transition from molecular-scale chemistry to collective phenomena in complex systems is also of interest, allowing knowledge gained at the molecular level to be exploited through the dynamics and kinetics of collective interactions. In this manner, the desired evolution is toward predictive capabilities that span the microscopic to mesoscale domains enabling the computation of individual molecular interactions as well as their role in complex, collective behavior at continuum scales.

Some examples of recent awards managed in the CPIMS portfolio: (1) Studies of how applied electric fields influence ion hydration properties and water organization at the air/aqueous interface; (2) research that pushes accurate quantum simulations toward large mesoscale systems; (3) explorations of multidimensional infrared microscopy for visualizing chemical dynamics in heterogeneous environments; (4) investigations of photochemical reactions of relevance to chemical synthesis in charged micro-droplets; (5) theoretical studies of rare events in molecular simulations in aqueous systems, such as heterogeneous nucleation; (6) studies of ion solvation and charge transfer at complex interfaces using nonlinear soft x-ray spectroscopy; and (7) research on understanding chemical bond dynamics in solution using mixed quantum/classical molecular dynamics simulations.

To obtain a more detailed description about this research area, please see the Core Research Area description. A detailed snapshot of the program can be obtained by reading the proceedings of our Principal Investigators' Meetings. To better understand how this research area fits within the Department of Energy's Office of Science, please refer to the Basic Energy Science's organization chart and budget request.

The CPIMS program does not fund research in bulk fluid mechanics or fluid dynamics, applications such as the development of micro-scale devices, and research that is of principal importance to medical sciences and applications.

Other questions about this research area should be addressed by email to the Program Manager, Dr. Gregory Fiechtner.

Annual Meeting Books

Each year, the CPIMS program holds an annual meeting. The annual meeting books contain an abstract corresponding to each project that receives funding from the CPIMS program. Therefore, the books provide an informative snapshot of the program in time. You can download the four most recent books here:

Featured Research

Transient excitons at metal surfaces.

Excitons Detected in Metals by Multidimensional Photoemission Spectroscopy

Transient excitons have been observed in metals for the first time. Here, the surface electrons of silver crystals can maintain the excitonic state more than 100 times longer than for the bulk metal, enabling the excitons to be experimentally visualized by a newly developed, multidimensional coherent spectroscopic  technique.

X. Cui, C. Wang, A. Argondizzo, S. Garrett-Roe, B. Gumhalter, H. Petek, “Transient excitons at metal surfaces.”  Nature Physics 10, 505 (2014). [DOI: 10.1038/nphys2981]

X-Ray absorption spectroscopy of LiBF4 in propylene carbonate: a model lithium ion battery electrolyte.

X-Ray Absorption Spectroscopy of a Model Lithium Ion Battery Electrolyte

X-ray absorption spectroscopy was used to investigate the solvation structure of the lithium ion in propylene carbonate, a system similar to the liquid electrolyte within a lithium ion battery.  Theoretical calculations indicate that the lithium ion has a solvation number of 4.5, which is larger than expected based on the generally accepted tetrahedral coordination structure.

J. W. Smith, R. K. Lam, A. T. Sheardy, O. Shih, A. M. Rizzuto, O. Borodin, S. J. Harris, D. Prendergast, R. J. Saykally, “X-Ray absorption spectroscopy of LiBF4 in propylene carbonate: a model lithium ion battery electrolyte.” Phys. Chem. Chem. Phys. 16, 23568 (2014). [DOI: 10.1039/C4CP03240C]

Ultrafast imaging of surface plasmons propagating on a gold surface.

Ultrafast Imaging of Surface Plasmons Propagating on a Gold Surface

Time-resolved, nonlinear photoemission electron microscopy (PEEM) images of propagating surface plasmons (PSPs), launched from a lithographically patterned rectangular trench on a flat gold surface, have been recorded. Power-dependent PEEM images provide experimental evidence for a sequential coherent nonlinear photoemission process, in which one laser source launches a PSP through a linear interaction, and the second subsequently probes the PSP via two-photon photoemission. PEEM images reveal that the launched PSP may be detected at least 250 microns away from the coupling trench structure.

Y. Gong, A.G. Joly, D. Hu, P.Z. El-Khoury, W.P. Hess, “Ultrafast imaging of surface plasmons propagating on a gold surface.” Nano Letters 15, 3472 (2015). [DOI: 10.1021/acs.nanolett.5b00803]

Controlling surface reactions with nanopatterned surface elastic strain.

Controlling Surface Reactions with Nanopatterned Surface Elastic Strain

An array of intense, locally varying strain fields on a TiO2 (110) surface was created by introducing highly pressurized argon nanoclusters at 6-20 monolayers under the surface. Our results provide direct evidence of the influence of strain on atomic-scale surface chemical properties, and such effects may help guide future research in catalysis materials  design.

Z. Li, D. V. Potapenko, R. M. Osgood, “Controlling surface reactions with nanopatterned surface elastic strain.” ACS Nano 9, 82 (2015). [DOI:10.1021/nn506150m]

Elucidating the mechanism behind the stabilization of multi-charged metal cations in water: a case study of the electronic states of microhydrated Mg2+, Ca2+ and Al3+.

Stabilization Mechanism of Multi-Charged Metal Cations in Water

Replacing lithium with other metals with multiple charges could greatly increase battery capacity. But first researchers need to understand how to keep multiply charged ions stable. The paths that lead to either the hydrolysis of water or the creation of stable metal ion clusters, peaceably surrounded by water, have been determined. It comes down to the pH of the solution, the number of water molecules nearby, and the ionization potential.

E. Miliordos, S. S. Xantheas, “Elucidating the mechanism behind the stabilization of multi-charged metal cations in water: a case study of the electronic states of microhydrated Mg2+, Ca2+ and Al3+.” Phys. Chem. Chem. Phys. 16, 6886 (2014). [DOI: 10.1039/C3CP53636J]

The Influence of Cholesterol on Fast Dynamics Inside of Vesicle and Planar Phospholipid Bilayers Measured with 2D IR Spectroscopy.

Fast Dynamics inside Phospholipid Bilayers Measured with 2D IR Spectroscopy

2D IR vibrational echo spectroscopy was performed on the antisymmetric CO stretch of vibrational probe molecules, which are located in the interior alkyl regions of phospholipid bilayers. The measurements show that the bilayer interior alkyl region dynamics occur on time scales ranging from a few to many tens of picoseconds. The results suggest that at least a significant fraction of the bilayers’ structural dynamics arise from density fluctuations.

O. Kel, A. Tamimi, M. D. Fayer, “The Influence of Cholesterol on Fast Dynamics Inside of Vesicle and Planar Phospholipid Bilayers Measured with 2D IR Spectroscopy.” J. Phys. Chem. B 119, 8852 (2015). [DOI: 10.1021/jp503940k]

Thermodynamic Driving Forces for Dye Molecule Position and Orientation in Nanoconfined Solvents.

Thermodynamic Driving Forces in Nanoconfined Solvents

Replica exchange molecular dynamics simulations of a dye molecule dissolved in ethanol, confined within a 2.4 nm hydrophilic amorphous silica pore, are presented. The dye position and orientation distributions provide insight into time-dependent fluorescence measurements in nanoconfined solvents as well as general features of chemistry in mesoporous materials.

J. A. Harvey, W. H. Thompson, “Thermodynamic Driving Forces for Dye Molecule Position and Orientation in Nanoconfined Solvents.” J. Phys. Chem. B 119, 9150 (2015). [DOI:10.1021/jp509051n]

Probing the photochemistry of chemisorbed oxygen on TiO2(110) with Kr and other co-adsorbates.

Probing the Photochemistry of Chemisorbed Oxygen with Krypton Co-Adsorbates

In a study that, to our knowledge, is the first evidence for photo-activity of oxygen adatams on TiO2(110), weakly-bound species, such as Kr, CO2, and N2, were used to probe the photochemistry of chemisorbed oxygen on TiO2(110). The results point to a new tool for studying photochemical processes on surfaces.

N. G. Petrik, G. A. Kimmel, “Probing the photochemistry of chemisorbed oxygen on TiO2(110) with Kr and other co-adsorbates.” Phys. Chem. Chem. Phys. 16, 2338 (2014). [DOI: 10.1039/c3cp54195a]

Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe.

Real-Space Imaging of Molecular Structure and Chemical Bonding

A new and generally applicable technique based on the scanning tunneling microscope (STM) provides real space images of molecular structures. A tip terminated with a single carbon monoxide (CO) molecule was scanned over a single cobalt-phthalocyanine (CoPc) molecule adsorbed on Ag(110) surface at 600 mK while monitoring the hindered translational vibration of the CO. The variation in the vibrational intensity in the scan provides the contrast in the CoPc skeletal structure due to the CO molecule sensing the electrostatic potential inside the CoPc. Such images provide an understanding into the relation of structure and function of molecules.

C. Chiang, C. Xu, Z. Han, W. Ho, “Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe.” Science 344, 885 (2014). [DOI:10.1126/science.1253405]

Water vibrations have strongly mixed intra- and intermolecular character.

Water Vibrations have Strongly Mixed Intra- and Intermolecular Character

Using a new sub-70-femtosecond, broadband mid-infrared source, we performed two-dimensional infrared, transient absorption and polarization anisotropy spectroscopy of liquid water by exciting the OH stretching transition and characterizing the response from 1,350 cm−1 to 4,000 cm−1. Such results change the way that molecular vibrations in water are perceived, which significantly impacts future discussion of aqueous chemical reactions.

K. Ramasesha, L. De Marco, A. Mandal, A. Tokmakoff, “Water vibrations have strongly mixed intra- and intermolecular character.” Nature Chemistry 5, 935 (2013). [DOI: 10.1038/nchem.1757]

Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster.

Vibrational Signature of the Proton Defect in a Three-Dimensional Hydrogen Bonded Water Network

Cryogenic ion vibrational predissociation (CIVP) spectroscopy has been used to solve a long-standing puzzle regarding the vibrational signature of the proton defect in the “magic number” H+(H2O)21 cluster ion. The new information was obtained by first slowly cooling the parent ion in a 10K RF ion trap, where weakly bound D2 molecules were attached prior to vibrational excitation in a photofragmentation mass spectrometer. By combining the photon energy range accessible with table top and free electron lasers (Fritz Haber Institute, Asmis group), spectra were obtained from 200  to 4,000 cm-1, thus providing an unprecedented spectroscopic view of an archetypal, three dimensional H-bonded water network.

J. A. Fournier, C. J. Johnson, C. T. Wolke, G. H. Weddle, A. B. Wolk, M. A. Johnson, “Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster.”  Science 344, 1009 (2014).  [DOI: 10.1126/science.1253788]

Persistent ion pairing in aqueous hydrochloric acid.

Persistent Ion Pairing in Aqueous Hydrochloric Acid

Improving chemical reactions ranging from refining oil to building longer-lasting batteries means understanding the chemistry of acids and bases. Researchers discovered that when a strong acid such as hydrochloric acid (HCl) is mixed with water, the negatively charged anion and positively charged cation remain close and create an unexpected structure. These results provide a better understanding of the complexity of acid/base chemistry in concentrated, non-ideal chemical solutions.

M.D. Baer, J.L. Fulton, M. Balasubramanian, G.K. Schenter, C.J. Mundy, “Persistent ion pairing in aqueous hydrochloric acid.” The Journal of Physical Chemistry B 118, 7211 (2014). [DOI: 10.1021/jp501091h]

The hydration structure of dissolved carbon dioxide from X-ray absorption spectroscopy.

The Importance of Hydration

In people, phytoplankton, and in fact in all living organisms, water’s pH – acidic, basic, or neutral – has a profound effect. Water often becomes acidic because of contacting gaseous carbon dioxide in the atmosphere. When the carbon dioxide dissolves in the water, it forms carbonic acid. DOE Scientists characterized the structure of carbon dioxide in water. They found that the dissolved carbon dioxide bonds only very weakly to the surrounding water, but creates a cylindrical cavity in the liquid.

R. K. Lam, A. H. England, J. W. Smith, A. M. Rizzuto, O. Shih, D. Prendergast, R. J. Saykally, “The hydration structure of dissolved carbon dioxide from X-ray absorption spectroscopy.” Chemical Physics Letters 633, 214 (2015). [DOI: 10.1016/j.cplett.2015.05.039]