AI Article Synopsis
- The Eckart conditions are crucial for accurately separating rotation and vibration in rovibrational level computations and spectroscopic intensities.
- Dymarsky and Kudin's method for simplifying the Eckart rotation matrix has been adapted to develop a kinetic energy operator in curvilinear coordinates without using finite differences.
- This new approach enables effective analysis of complex molecular systems like HONO, allowing for simultaneous calculation of rotational levels, frequencies, and infrared spectra intensities for both isomers using multiple reference geometries.
Article Abstract
For the computation of rovibrational levels and their spectroscopic intensities, the Eckart conditions are essential to achieve the optimal separation between rotation and vibration. Dymarsky and Kudin [J. Chem. Phys. 122, 124103 (2005)] proposed a procedure for a simplified calculation of the Eckart rotation matrix. In the present work, we have adapted their approach to obtain a kinetic energy operator in curvilinear coordinates using a numerical but exact procedure without resorting to finite differences. Furthermore, we have modified this approach for the study of molecular systems with several minima, for which several Eckart reference geometries are required. The HONO molecular system has been used to show the efficiency of our implementation. Using the Eckart conditions with multi-reference geometries allows for a calculation of the rotational levels as well as frequencies and intensities of the infrared spectra of both HONO isomers with a single calculation.
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| http://dx.doi.org/10.1063/1.4942172 | DOI Listing |
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