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Unveiling the structure, dynamics and spectral properties of aqueous clusters: A new theoretical approach

EMSL Project ID


Elucidating the nature of aqueous solvation and in particular of
hydrogen bonding are important for understanding chemical reactions in
the atmosphere and at aqueous interfaces. Infrared (IR) and
photoelectron spectroscopy (PES) of molecular clusters have proven
valuable in this respect. However, despite a number of recent successes
there remain many open questions. In particular, the interpretation and
understanding of the complex results requires a close cooperation
between experiment and theory. We propose here the development of a new
theoretical protocol for the calculation of infrared and photoelectron
spectra that (i) produces full infrared and photoelectron spectra, (ii)
includes anharmonicity and dynamics in a natural manner, and (iii) is
widely applicable to molecular clusters. Our approach is based on
combining highly correlated levels of ab-initio electronic structure
theory with quasi-classical molecular dynamics simulations. This
combination has proven successful for the simulation of the IR and PES
spectra in recent applications. We will utilize the supercomputer
resources and experimental results obtained at EMSL to develop, test and
benchmark the proposed protocol.

Project Details

Project type
Exploratory Research
Start Date
End Date


Principal Investigator

Martin Head-Gordon
University of California, Berkeley

Team Members

Daniel Lambrecht
University of Pittsburgh

Karol Kowalski
Pacific Northwest National Laboratory

Sotiris Xantheas
Pacific Northwest National Laboratory

Related Publications

Mardirossian N, DS Lambrecht, L McCaslin, SS Xantheas, and MP Head-Gordon. 2013. "The Performance of Density Functionals for Sulfate-Water Clusters." Journal of Chemical Theory and Computation 9(3):1368-1380. doi:10.1021/ct4000235
Sams RL, SS Xantheas, and TA Blake. 2012. "Vapor Phase Infrared Spectroscopy and ab initio Fundamental Anharmonic Frequencies of Ammonia Borane." Journal of Physical Chemistry A.