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Quantum molecular dynamics simulations of liquid benzene using orbital optimization

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Abstract

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.

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Acknowledgments

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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  1. Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA

    Nazar Ileri & Laurence E. Fried

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  1. Nazar Ileri
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  2. Laurence E. Fried
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Correspondence to Laurence E. Fried.

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Dedicated to Professor Greg Ezra and published as part of the special collection of articles celebrating his 60th birthday.

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Ileri, N., Fried, L.E. Quantum molecular dynamics simulations of liquid benzene using orbital optimization. Theor Chem Acc 133, 1575 (2014). https://doi.org/10.1007/s00214-014-1575-5

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