caa a22 4500 605511985 CHVBK 20210128100653.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00894-015-2628-y doi (NATIONALLICENCE)springer-10.1007/s00894-015-2628-y Water-assisted isomerization of the [H, C, N, O] system [Elektronische Daten] [Jia Cao, Zhi Wang, Lou Gao, Feng Fu] Ten minima of [H, C, N, O] isomers were investigated in gas phase and water solution using the polarizable continuum model at the CCSD(T)//M06-2X/6-311 + G(3df,2p) level of theory. The results show that the stability order of all isomers in water solution is HNCO > HOCN > HCNO > HONC > Y-OC(H)N > cycl-OCN(H)-a ≈ cycl-OCN(H)-b > cycl-NCO(H) > HNOC > HCON, i.e., the same as that in the gas phase. Potential energy surfaces of [H, C, N, O] system isomerization were constructed in gas phase and in water solution, showing that the isomerization of [H, C, N, O] isomers in gas phase is unfavorable because of the high barrier height. Interestingly, although the water solvent has alittle impact on the isomeric mechanism, water molecules (H2O)n(n = 1-3) acting as catalyst dramatically lower the barrier height in the hydrogen transfer processes (HCNO → HONC, HNCO → HOCN, and HCON → HNOC). Water is the most abundant compound in the interstellar area. These results give new insight into the mechanism of [H, C, N, O] system isomerization in interstellar gas. Enthalpies of formation of the isomers were predicted at the CBS-QB3, G4MP2 and W1U levels. Graphical Abstract Electron location function (ELF) maps of species in the isomerization from HCNO to HONC at the M06-2X/6-311+G(3df,2p) level. Regions of greatest and smallest localization electron densityare colored red and blue, respectively Springer-Verlag Berlin Heidelberg, 2015 [H, C, N, O] isomers nationallicence Isomeric mechanism nationallicence Water-assisted nationallicence Cao Jia College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut Wang Zhi College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut Gao Lou College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut Fu Feng College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-8 1610-2940 21:3<1 2015 21 894 https://doi.org/10.1007/s00894-015-2628-y text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2628-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Cao Jia College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut NATIONALLICENCE 700 1- Wang Zhi College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut NATIONALLICENCE 700 1- Gao Lou College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut NATIONALLICENCE 700 1- Fu Feng College of Chemistry and Chemical Engineering, Yan'an University, 716000, Shaanxi, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-8 1610-2940 21:3<1 2015 21 894