Vibration–rotation transition dipoles from first principles

2014/02/04 by Jonathan Tennyson · 10 citations
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Ab initio #Advanced Chemical Physics Studies #Atmospheric Ozone and Climate #Atomic physics #Computer science #Dipole #Moment (physics) #Physics #Potential energy #Potential energy surface #Quantum #Quantum mechanics #Rotation (mathematics) #Spectroscopy and Laser Applications #Transition dipole moment #Vibration

paper · pdf · doi:10.1016/j.jms.2014.01.012

openalex publication_date 2014/02/04 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/31

Abstract

The use of ab initio methods to calculate line positions and associated transition intensities for the infrared spectrum of small molecules has recently become common. The first principles calculation of transition dipoles, upon which the intensity is based, relies on three distinct steps: the quantum chemical calculation of the dipole moment surface at a grid of geometries, the accurate representation of this surface using an appropriate functional form and the wave functions used to represent the initial and final states, which in turn depend on the accuracy of the potential energy surface used to generate them. Each of these stages is discussed with a view to obtaining the highest possible accuracy. The prospect of computed transition intensities displacing measured ones as the primary source of such information is considered.

Citations

• HITEMP, the high-temperature molecular spectroscopic database

Cited by

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• The Cologne Database for Molecular Spectroscopy, CDMS, in the Virtual Atomic and Molecular Data Centre, VAMDC
• ExoMol linelists XXVIII: the rovibronic spectrum of AlH
• ExoMol line lists XXV: a hot line list for silicon sulphide, SiS
• Potential energy surface, dipole moment surface and the intensity calculations for the 10 µm, 5 µm and 3 µm bands of ozone
• Theoretical rotation-vibration spectroscopy of cis- and trans-diphosphene (P2H2) and the deuterated species P2HD
• Water vapor [wikipedia]

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