Electronic Structure Theory

The Aspuru-Guzik group’s contributions to electronic structure involve the development of methods to apply quantum chemical calculations to the description of new types of quantum processes. Early work developed fast electron correlation codes exploiting GPU hardware to address larger systems. This was followed by an electrostatic embedding scheme, ChEESE (Chemistry in Electrostatic Environments). The existence of at time-dependent density functional theory for systems interacting with a bath was proven, and demonstrative applications were shown. Several applications of electronic structure have been made to Surface-Enhanced Raman spectroscopy, and more recently to combinatorial thermochemistry.

New methodologies under development include a self-interaction corrected functional which provides a derivative discontinuity for DFT. This provides better ionization energies than simple GGA’s, and comes at a cost lower than the calculation of exact exchange. There is also work to unite electron-correlation perturbation theories with system-bath perturbation theories via the Lang-Firsov transformation and provide an ab-initio system-bath theory of electronic dynamics.


Representative Publications
  1. Dmitrij Rappoport, Sangwoo Shim, and Alán Aspuru-Guzik. Simplified Sum-Over-States Approach for Predicting Resonance Raman Spectra. Application to Nucleic Acid Bases. The Journal of Physical Chemistry Letters 2, no. 11 (June 2, 2011): 1254–1260.
  2. Roberto Olivares-Amaya, Michael Stopa, Xavier Andrade, Mark A. Watson, and Alán Aspuru-Guzik. Anion Stabilization in Electrostatic Environments. The Journal of Physical Chemistry Letters 2, no. 7 (April 7, 2011): 682–688.
  3. Semion K. Saikin, Yizhuo Chu, Dmitrij Rappoport, Kenneth B. Crozier, and Alán Aspuru-Guzik. Separation of Electromagnetic and Chemical Contributions to Surface-Enhanced Raman Spectra on Nanoengineered Plasmonic Substrates. The Journal of Physical Chemistry Letters 1, no. 18 (September 16, 2010): 2740–2746.
  4. Mark Watson, Roberto Olivares-Amaya, Richard G. Edgar, and Alán Aspuru-Guzik. Accelerating Correlated Quantum Chemistry Calculations Using Graphical Processing Units. Computing in Science & Engineering 12, no. 4 (July 2010): 40–51.
  5. Kenta Hongo, Mark A. Watson, Roel S. Sánchez-Carrera, Toshiaki Iitaka, and Alán Aspuru-Guzik. Failure of Conventional Density Functionals for the Prediction of Molecular Crystal Polymorphism: A Quantum Monte Carlo Study. The Journal of Physical Chemistry Letters 1, no. 12 (June 17, 2010): 1789–1794.
  6. Joel Yuen-Zhou, David G. Tempel, César A. Rodríguez-Rosario, and Alán Aspuru-Guzik. Time-Dependent Density Functional Theory for Open Quantum Systems with Unitary Propagation. Physical Review Letters 104, no. 4 (January 2010).
  7. Roberto Olivares-Amaya, Mark A. Watson, Richard G. Edgar, Leslie Vogt, Yihan Shao, and Alán Aspuru-Guzik. Accelerating Correlated Quantum Chemistry Calculations Using Graphical Processing Units and a Mixed Precision Matrix Multiplication Library. Journal of Chemical Theory and Computation 6, no. 1 (January 12, 2010): 135–144.