Anharmonic Calculation of the Structure, Vibrational Frequencies and Intensities of the NH3 center dot center dot center dot trans-HONO Complex

作者：Bulychev Valentin P; Buturlimova Marina V; Tokhadze Konstantin G^*

来源：Journal of Physical Chemistry A, 2013, 117(37): 9093-9098.

DOI：10.1021/jp406569y

The equilibrium geometry of the NH3 center dot center dot center dot trans-HONO complex and the harmonic vibrational frequencies and intensities are calculated in the MP2/aug-cc-pVTZ approximation with the basis set superposition error taken into account. Effects of anharmonic interactions on spectroscopic parameters are studied by solving vibrational Schrodinger equations in 1-4 dimensions using the variational method. Anharmonic vibrational equations are formulated in the space of normal coordinates of the complex. Detailed analysis is performed for the H-bond stretching vibration and internal vibrations of the trans-MONO isomer in the complex. The intermode anharmonicity and anharmonic coupling between two, three, and four vibrational modes are studied on the basis of correct ab initio potential energy surfaces calculated in the above approximation. The combinations of normal modes of the complex most strongly coupled to one another are examined. The calculated frequencies and intensities of vibrational bands are compared with the experimental data on the NH3 center dot center dot center dot trans-HONO complex in an argon matrix and results of earlier calculations of monomeric HONO. In this calculation the strong resonance between the first excited state of the OH stretching vibration and the doubly excited state of the NOH bending vibration of trans-HONO isomer in the complex is thoroughly studied by solving vibrational equations in two and four dimensions.

• 出版日期2013-9-19