Nature of infrared-active phonon sidebands to internal vibrations: Spectroscopic studies of solid oxygen and nitrogen

Abstract

The ir-active phonon sidebands to internal vibrations of oxygen and nitrogen were precisely investigated by Fourier transform infrared spectroscopy in the fundamental and first overtone spectral regions from 10 K to the boiling points at ambient pressure. We showed that an analysis of ir-active phonon sidebands yields important information on the internal vibrations of molecules in a condensed medium (solid or liquid), being complementary to Raman data on vibron frequencies. Analyzing the complete profile of these bands, we determined the band origin frequencies and explored their temperature behavior in all phases of both substances. We present unambiguous direct experimental proofs that this quality corresponds to the frequency of internal vibrations of single molecules. Considering solid oxygen and nitrogen as two limiting cases for simple molecular solids, we interpret this result as a strong evidence for a general fact that an ir-active phonon sideband possesses the same physical origin in pure molecular solids and in impurity centers. The key characteristics of the fundamental vibron energy zone (environmental and resonance frequency shifts) were deduced from the combined analysis of ir and Raman experimental data and their temperature behavior was explored in solid and liquid phases of oxygen and nitrogen at ambient pressure. The character of the short-range orientational order was established in the \ensuremath{\beta}-nitrogen based on our theoretical analysis consistent with the present experimental results. We also present the explanation of the origin of pressure-caused changes in the frequency of the Raman vibron mode of solid oxygen at low temperatures.