@Article{CorreaSilvBarrAlbe:2017:ThStH,
               author = "Correa, Eberth and Silva, Washington Barbosa da and Barreto, 
                         Patr{\'{\i}}cia Regina Pereira and Albernaz, Alessandra F.",
          affiliation = "{Universidade de Bras{\'{\i}}lia (UNB)} and Instituto Federal de 
                         Educa{\c{c}}{\~a}o, Ci{\^e}ncia e Tecnologia de Goi{\'a}s and 
                         {Instituto Nacional de Pesquisas Espaciais (INPE)} and 
                         {Universidade de Bras{\'{\i}}lia (UNB)}",
                title = "Theoretical study of the H + HCN \−\→ H + HNC 
                         process",
              journal = "Journal of Molecular Modeling",
                 year = "2017",
               volume = "23",
               number = "5",
                month = "May",
             keywords = "H + HCN reaction, Master equation method, Thermal rate constants, 
                         Transition state theory.",
             abstract = "We present a theoretical study on the detailed mechanism and 
                         kinetics of the H + HCN \→ H + HNC process. The potential 
                         energy surface was calculated at the complete basis set quantum 
                         chemical method, CBS-QB3. The vibrational frequencies and 
                         geometries for four isomers (H 2CN, cis-HCNH, trans-HCNH, CNH 2), 
                         and seven saddle points (TSn where n = 1 \− 7) are very 
                         important and must be considered during the process of formation 
                         of the HNC in the reaction were calculated at the 
                         B3LYP/6-311G(2d,d,p) level, within CBS-QB3 method. Three different 
                         pathways (PW1, PW2, and PW3) were analyzed and the results from 
                         the potential energy surface calculations were used to solve the 
                         master equation. The results were employed to calculate the 
                         thermal rate constant and pathways branching ratio of the title 
                         reaction over the temperature range of 300 up to 3000 K. The rate 
                         constants for reaction H + HCN \→ H + HNC were fitted by 
                         the modified Arrhenius expressions. Our calculations indicate that 
                         the formation of the HNC preferentially occurs via formation of 
                         cisHCNH, the fitted expression is kPW2(T) = 9.98 × 
                         10\−22T2.41 exp(\−7.62 kcal.mol\−1/RT) while 
                         the predicted overall rate constant kOverall(T) = 9.45 × 
                         10\−21T2.15 exp(\−8.56 kcal.mol\−1/RT) in cm3 
                         molecule\−1s\−1.",
                  doi = "10.1007/s00894-017-3335-7",
                  url = "http://dx.doi.org/10.1007/s00894-017-3335-7",
                 issn = "1610-2940",
             language = "en",
           targetfile = "correa_theoretical.pdf",
        urlaccessdate = "27 abr. 2024"
}