Theoretical Chemistry Accounts

, 133:1575 | Cite as

Quantum molecular dynamics simulations of liquid benzene using orbital optimization

  • Nazar Ileri
  • Laurence E. Fried
Regular Article
Part of the following topical collections:
  1. Ezra Festschrift Collection


The structure of liquid benzene is investigated by quantum molecular dynamics simulations. Results using variationally optimized numerical pseudo-atomic orbitals are compared to those of generic optimized orbitals. The accuracy of the first-principle calculations is compared with recent experimental findings. Simulations using minimal basis sets with optimized orbitals are shown to successfully predict the local structure of liquid benzene, while simulations with non-optimized minimal basis sets have significant errors in the structure of the first solvation shell. The use of a minimal optimized basis set considerably speeds up simulations, while preserving much of the accuracy of a larger basis set formed by generic orbitals. The transferability of the optimized orbitals is also explored under different environmental conditions.


Liquid benzene Ab initio simulations Orbital optimization Krylov Direct diagonalization 



This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Laurence E. Fried thanks Prof. Gregory S. Ezra for his patient encouragement and guidance at Cornell University.


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Copyright information

© Springer-Verlag Berlin Heidelberg (outside the USA) 2014

Authors and Affiliations

  1. 1.Physical and Life Sciences DirectorateLawrence Livermore National LaboratoryLivermoreUSA

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