Abstract

Water and hydrogen cyanide are two of the most common species in space and the atmosphere with the ability of binding to form dimers such as H2O-HCN. In the literature, while calculations characterizing various properties of the H2O-HCN cluster (equilibrium distance, vibrational frequencies and rotational constants) have been done in the past, extensive calculations of the rovibrational states of this system using a reliable quantum dynamical approach have yet to be reported. In this work, we intend to mend that by performing the first calculation of the rovibrational states of the H2O-HCN van der Waals complex on a recently developed potential energy surface. We use the block improved relaxation procedure implemented in the Heidelberg Multiconfiguration Time-Dependent Hartree (MCTDH) package to compute the states of the H2O-HCN isomer, from which we extract the transition frequencies and rotational constants of the complex. We further adapt an approach first suggested by Wang and Carrington—and supported here by analysis routines of the Heidelberg MCTDH package—to properly characterize the computed rovibrational states. The subsequent assignment of rovibrational states was done by theoretical analysis and visual inspection of the wavefunctions. Our simulations provide a Zero Point Energy (ZPE) and intermolecular vibrational frequencies in good agreement with past ab initio calculations. The transition frequencies and rotational constants obtained from our simulations match well with the available experimental data. This work has the broad aim to propose the MCTDH approach as a reliable option to compute and characterize rovibrational states of van der Waals complexes such as the current one.

Department(s)

Chemistry

Comments

U.S. Department of Energy, Grant AF-16/20-04

International Standard Serial Number (ISSN)

1463-9076

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2023 Royal Society of Chemistry, All rights reserved.

Publication Date

01 Jan 2023

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