Electronic and vibrational spectroscopy of ethyl methyl carbonate: A comparative experimental and theoretical study. (September 2021)

• Record Type: Journal Article
• Authors: Das, Asim Kumar; Sunanda, K.; Rajasekhar, B.N.
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 272(2021)
• Publication Date: 2021-09
• Subjects: Ethyl methyl carbonate -- Infrared spectra -- Vacuum ultraviolet absorption -- Synchrotron radiation -- Rydberg series -- TDDFT; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2021.107789
• Languages: English
• ISSNs: 0022-4073

Abstract

Highlights: First report of VUV spectrum in 7 – 11.5eV energy region. Electronic spectrum assigned to valence and Rydberg series converging to first four ionization potential aided with quantum chemical stimulations. First report predicted of fundamental vibrational modes and assignment of infrared spectra in 5004000 cm −1 region. Interpretation of diffuse electronic spectra from study of low lying potential energy curves. Abstract: A detailed spectroscopic study on ethyl methyl carbonate, a green solvent, has been carried out by recording vacuum ultraviolet and infrared spectra. The vacuum ultraviolet photoabsorption spectrum is recorded using synchrotron radiation from Photophysics beamline at the Indus-1 synchrotron radiation source at RRCAT, Indore, India in the wavelength region of 7–11.5 eV. Infrared spectra in gas phase as well as matrix isolated case are recorded using an indigenously developed laboratory low temperature experimental facility and a Fourier transform infrared spectrometer in the 500–4000 cm −1 region. Geometry optimization, vibrational frequency analysis of neutral & ionized ethyl methyl carbonate and electronic excited state energy information has been obtained using quantum chemical calculations. The observed ir spectral features could be assigned to the fundamental vibrational modes of the molecule. The vacuum ultraviolet region comprising a broad continuum is assigned to valence transitions having high oscillator strengths and overlying weak bands to ns, np, nd type Rydberg transitions. Potential energy curves of the ground and first few low lying excited states generated provided additional insights into their nature and further interpretation of observed experimental spectra. In this paper we report the first electronic absorption spectrum in 7 to 11.5 eV region, its spectroscopic analysis and identification of vibrational modes in the infrared spectra for ethyl methyl carbonate. Results of quantum chemical simulations carried out to obtain nature of excited states, energies and vibrational frequencies using GAMESS (USA) quantum chemistry code are also reported in this paper.