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Kolekcje
Inne
Effect of conformational isomerism on NIR spectra of ethanol isotopologues. Spectroscopic and anharmonic DFT study.
Autorzy
Rok wydania
2020
Czasopismo
Numer woluminu
310
Strony
113271/1-113271/11
DOI
10.1016/j.molliq.2020.113271
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Effect of isotopic substitution on near-infrared (NIR) spectra has not been a subject of systematic studies. NIR spectra even relatively simple molecules are very complex, and therefore a detailed interpretation of spectral changes in this region is a challenging task. Recent progress in anharmonic quantum mechanical calculations allows for accurate simulation of NIR spectra. Here, we present a systematic study of the effect of isotopic substitution on NIR spectra of ethanol. To obtain a comprehensive understanding of NIR spectra we considered both different conformations (gauche, trans) and isotopologues (CX3CX2OX; X = H, D) of ethanol. The anharmonic calculations were based on generalized vibrational second-order perturbation theory (GVPT2) at DFT-B2PLYP/def2-TZVP level. Simulations included the first and second overtones, as well as binary and ternary combinations bands. This way we successfully reproduced even fine features in the spectra of diluted (0.1 M in CCl4) samples. Additionally, we demonstrated the potential of anharmonic calculations in predicting the spectra of the samples, which are not commercially available (CH3CD2OD and CD3CH2OD). Our results reveal complex nature of the changes in NIR spectra of ethanols due to coexistence of structural and isotopic effects.
Słowa kluczowe
Near-infrared (NIR) spectroscopy, Anharmonic quantum chemical calculations, GVPT2, Isotopic substitution, Conformers, Overtones and combinations bands, Ethanol
Adres publiczny
http://dx.doi.org/10.1016/j.molliq.2020.113271
Strona internetowa wydawcy
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