Global reaction route mapping of isomerization pathways of exotic C6H molecular species

• Published in: The Journal of chemical physics 2013-12, Vol.139 (22), p.224311-224311
• Main Authors: Vikas, Kaur, Gurpreet
• Format: Article
• Language: English
• Subjects: Anharmonicity; Isomerization; Isomers; Mapping; Orbital stability; Physics; Potential energy; Raman spectra; Rotational spectra; Searching; Stability analysis; Substitution reactions
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4840755

C6H radical is known to exist in the astrophysical environment in linear form; however, it may originate from nonlinear isomeric forms. Potential energy surface of C6H is explored to search isomers of C6H and transition states connecting them. This work reports first-ever identification of reaction pathways for isomerization of C6H. The reaction route search is performed through global reaction route mapping method, which utilizes an uphill walking technique based on an anharmonic downward distortion following approach to search intermediates and transition states. The computations performed at the CASSCF∕aug-cc-pVTZ, CCSD(T)∕6-311++G(d,p)∕∕DFT∕B3LYP∕6-311++G(d,p), and DFT∕B3LYP∕aug-cc-pVTZ levels of the theory identified 14 isomers (including 8 new isomeric forms of C6H) and 28 transition states. Most of the identified isomers are found to have significant multireference character. The kinetic stability and natural bond orbital analysis of the identified isomers is also investigated. The isomeric forms are further characterized using spectral analysis involving rotational constants, vibrational frequencies, and Raman scattering activities as well as analyzing the effect of isotopic substitution of hydrogen on the spectral features. This study proposes that the linear-C6H can readily isomerize to a six-member ring isomer.