Methylcyanopolyynes (CH3-[C≡C]n-CN) are a particular kind of linear molecular wires, where the first three oligomers have been detected in the interstellar medium, particularly in CW Leonis (IRC + 10216), as well as ...Methylcyanopolyynes (CH3-[C≡C]n-CN) are a particular kind of linear molecular wires, where the first three oligomers have been detected in the interstellar medium, particularly in CW Leonis (IRC + 10216), as well as in the envelopes of carbon-rich stars in a similar way to the unsubstituted cyanopolyynes. Based on the projected natural distribution in cold clouds under LTE, we have determined the radial column density of new expected methylcyanopolyynes to be present in CW Leonis (IRC + 10216). By following, we have made use of the inner molecular resistances of the internal charge transfer process presenting in these oligomeric species in order to determine the reactivity trends between them. Therefore, geometrical parameters and dipole moments determinations for these methylcyanopolyynes involving the n = 1 to 14 molecular species were obtained from Ab initio molecular orbital calculations by means of a GAUSSIAN Program, using a restricted Hartree-Fock approach and 6-311G* basis set. Our results present a similar behavior observed in cyanopolyynes, where this series reaches a saturation level at the 14th oligomer with a maximum dipole moment of 8.21 ± 0.01 (Debyes). Thus, this molecular wire model permits us to comprehend how these methylcyanopolyynes reach a maximum length in such chemical environment, in agreement to the astronomical observations and cosmological chemical models. The following CH3C9N and CH3C11N oligomers in CW Leonis should be expected near to 3.52 × 1010 [cm2] and 1.82 × 1010 [cm2], respectively.展开更多
Cyanopolyynes (H[C≡C]n-CN or HC2n+1N, where n = 1, 2, 3, …, n) are commonly observed in the interstellar medium (ISM) as well as in the envelopes of carbon-rich stars. These linear molecular structures can be well d...Cyanopolyynes (H[C≡C]n-CN or HC2n+1N, where n = 1, 2, 3, …, n) are commonly observed in the interstellar medium (ISM) as well as in the envelopes of carbon-rich stars. These linear molecular structures can be well described with a one-dimensional conduction model, which considers the scattering processes of electrons through the charge transfer conduction bridge of the H[C≡C]n-molecular wire containing the CN group as an electron-acceptor terminal unit. Therefore, our results using this model enable a better understanding of the longest molecules observed in interstellar space and provide new insight into why these particular cyanopolyynes reach a maximum length, such as is observed from astronomical experimental spectral data and cosmological chemical models. Dipole moments and geometrical parameters of these cyanopolyynes were obtained from ab initio molecular orbital calculations using the restricted Hartree-Fock approach and 6-311G* basis set, in order to obtain the inner resistance as a new parameter of chemical reaction feasibility for this molecular series. Using this last molecular parameter, we have been able to analyze the possibility of identifying long molecular species that can be found under local thermodynamic equilibrium in some ISM such us HC25H, HC27H, and HC29N, which have not been observed at present.展开更多
文摘Methylcyanopolyynes (CH3-[C≡C]n-CN) are a particular kind of linear molecular wires, where the first three oligomers have been detected in the interstellar medium, particularly in CW Leonis (IRC + 10216), as well as in the envelopes of carbon-rich stars in a similar way to the unsubstituted cyanopolyynes. Based on the projected natural distribution in cold clouds under LTE, we have determined the radial column density of new expected methylcyanopolyynes to be present in CW Leonis (IRC + 10216). By following, we have made use of the inner molecular resistances of the internal charge transfer process presenting in these oligomeric species in order to determine the reactivity trends between them. Therefore, geometrical parameters and dipole moments determinations for these methylcyanopolyynes involving the n = 1 to 14 molecular species were obtained from Ab initio molecular orbital calculations by means of a GAUSSIAN Program, using a restricted Hartree-Fock approach and 6-311G* basis set. Our results present a similar behavior observed in cyanopolyynes, where this series reaches a saturation level at the 14th oligomer with a maximum dipole moment of 8.21 ± 0.01 (Debyes). Thus, this molecular wire model permits us to comprehend how these methylcyanopolyynes reach a maximum length in such chemical environment, in agreement to the astronomical observations and cosmological chemical models. The following CH3C9N and CH3C11N oligomers in CW Leonis should be expected near to 3.52 × 1010 [cm2] and 1.82 × 1010 [cm2], respectively.
文摘Cyanopolyynes (H[C≡C]n-CN or HC2n+1N, where n = 1, 2, 3, …, n) are commonly observed in the interstellar medium (ISM) as well as in the envelopes of carbon-rich stars. These linear molecular structures can be well described with a one-dimensional conduction model, which considers the scattering processes of electrons through the charge transfer conduction bridge of the H[C≡C]n-molecular wire containing the CN group as an electron-acceptor terminal unit. Therefore, our results using this model enable a better understanding of the longest molecules observed in interstellar space and provide new insight into why these particular cyanopolyynes reach a maximum length, such as is observed from astronomical experimental spectral data and cosmological chemical models. Dipole moments and geometrical parameters of these cyanopolyynes were obtained from ab initio molecular orbital calculations using the restricted Hartree-Fock approach and 6-311G* basis set, in order to obtain the inner resistance as a new parameter of chemical reaction feasibility for this molecular series. Using this last molecular parameter, we have been able to analyze the possibility of identifying long molecular species that can be found under local thermodynamic equilibrium in some ISM such us HC25H, HC27H, and HC29N, which have not been observed at present.
