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Curve Crossing in a Manifold of Coupled Electronic States: Direct Quantum Dynamics Simulations of Formamide

Abstract

Quantum dynamics simulations are an important tool to evaluate molecular behaviour including the, often key, quantum nature of the system. In this paper we present an algorithm that is able to simulate the time-evolution of a molecule after photo-excitation into a manifold of states. The Direct Dynamics variational Multi-Configurational Gaussian (DD-vMCG) method circumvents the computational bottlenecks problems of traditional grid-based methods by computing the potential energy functions on-the-fly, i.e. only where required. Unlike other commonly used direct dynamics methods, DD-vMCG is fully quantum mechnical. Here, the method is combined with a novel on-the-fly diabatisation scheme to simulate the short-time dynamics of the key molecule formamide and its acid analogue formimidic acid. This is a challenging test system due to the nature and large number of excited-states and eight coupled states are included in the calculations. It is shown that the method is able to provide unbiased information on the product channels open after excitation at different energies and demonstrates the potential to be a practical scheme, limited mainly by the quality of the quantum chemistry used to describe the excited states.

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Publication details

The article was accepted on 15 May 2018 and first published on 16 May 2018


Article type: Paper
DOI: 10.1039/C8FD00090E
Citation: Faraday Discuss., 2018, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
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    Curve Crossing in a Manifold of Coupled Electronic States: Direct Quantum Dynamics Simulations of Formamide

    K. E. Spinlove, G. Richings, M. A. Robb and G. Worth, Faraday Discuss., 2018, Accepted Manuscript , DOI: 10.1039/C8FD00090E

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