Energetics and spectroscopic studies of CNO(‐)(H2O)n clusters and the temperature dependencies of the isomers: An approach based on a combined recipe of parallel tempering and quantum chemical methods

A system associated with several number of weak interactions supports numerous number of stable structures within a narrow range of energy. Often, a deterministic search method fails to locate the global minimum geometry as well as important local minimum isomers for such systems. Therefore, in this work, the stochastic search technique, namely parallel tempering, has been executed on the quantum chemical surface of the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msup><mml:mrow><mml:mtext>CNO</mml:mtext></mml:mrow> <mml:mrow><mml:mtext>(-)</mml:mtext></mml:mrow> </mml:msup> <mml:msub><mml:mrow><mml:mtext>(H</mml:mtext></mml:mrow> <mml:mrow><mml:mtext>2</mml:mtext></mml:mrow> </mml:msub> <mml:msub><mml:mrow><mml:mtext>O)</mml:mtext></mml:mrow> <mml:mrow><mml:mi>n</mml:mi></mml:mrow> </mml:msub> </mml:mrow> </mml:math> system for <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>n</mml:mi> <mml:mo>=</mml:mo> <mml:mn>1</mml:mn></mml:mrow> </mml:math> -8 to generate global minimum as well as several number of local minimum isomers. IR spectrum can act as the fingerprint property for such system to be identified. Thus, IR spectroscopic features have also been included in this work. Vertical detachment energy has also been calculated to obtain clear information about number of water molecules in several spheres around the central anion. In addition, in a real experimental scenario, not only the global but also the local minimum isomers play an important role in determining the average value of a particular physically observable property. Therefore, the relative conformational populations have been determined for all the evaluated structures for the temperature range between 20K and 400K. Further to understand the phase change behavior, the configurational heat capacities have also been calculated for different sizes.