Three-dimensional potential energy surface of the Ar-OH(2Pi i) complex

Area of Science:

• Physical Chemistry
• Spectroscopy
• Computational Chemistry

Background:

• Previous studies have investigated pure rotational transitions and rotation-vibration transitions of the Ar-OH complex.
• Understanding the intermolecular potential energy surface is crucial for characterizing the complex's dynamics and interactions.

Purpose of the Study:

• To simultaneously analyze diverse spectroscopic data to determine the ground-state potential energy surface of Ar-OH.
• To compare the determined potential energy surface with that of the isovalent Ar-SH complex.

Main Methods:

• Simultaneous analysis of pure rotational, rotation-vibration, and P-level structure transitions from various spectroscopic techniques.
• Numerical solution of the Schrodinger equation using the discrete variable representation method in Jacobi coordinates.
• Least-squares fitting of a three-dimensional potential energy surface using initial parameters from ab initio RCCSD(T) calculations.

Main Results:

• A refined three-dimensional potential energy surface for Ar-OH in its ground electronic state was determined.
• The analysis incorporated data from Fourier-transform microwave, infrared-ultraviolet double-resonance, and stimulated emission pumping spectroscopies.
• The determined potential energy surface shows dependence on the OH monomer bond length.

Conclusions:

• The study successfully determined the intermolecular potential energy surface of Ar-OH by integrating multiple spectroscopic datasets.
• The determined potential energy surface provides a more accurate description of the Ar-OH interaction.
• Comparison with Ar-SH offers insights into the effects of electronic structure on intermolecular potentials in radical complexes.