Theoretical studies on structures and stabilities of C₄H₂ ⁺ isomers

Abstract

The structures, energies, stabilities and spectroscopies of doublet C₄H₂ ⁺ cations were explored at the DFT/B3LYP/6-311G(d,p), CCSD(T)/6-311+G(2df,2pd)(single-point), and G3B3 levels. Ten minimum isomers including the chainlike, three-member-ring, and four-member-ring structures are interconverted by means of 15 interconversion transition states. The potential energy surface was investigated. At the CCSD(T)/6-311+G(2df,2pd) and G3B3 levels, the global minimum isomer was found to be a linear HCCCCH. The structures of the stable isomer and its relevant transition state are further optimized at the QCISD/6-311G(d,p) level. The bonding nature and structure of isomer HCCCCH were analyzed.

Keywords

C₄H₂ ⁺ / Potential energy surface / HCCCCH isomer

References

[1] Broadfoot A. L., Sandel B. R., Shemansky D. E., Holberg J. B., Smith G. R., Strobel D. F., McConnell J. C., Kumar S., Hunten D. M., Atreya S. K., Donahue T. M., Moos H. W., Bertaux J. L., Blamont J. E., Pomphrey R. B., Linick S. Science, 1981, 212: 206.

[2] Hanel R., Conrath B., Flasar F. M., Kunde V., Maguire W., Pearl J., Pirraglia J., Samuelson R., Herath L., Allison M., Cruikshank D., Gautier D., Gierasch P., Horn L., Koppany R., Ponnamperuma C. Science, 1981, 212: 192.

[3] Samuelson R., Nath N., Borysow A. Planet. Space Sci., 1997, 45: 959.

[4] Raulin F. Space Sci. Rev., 2008, 135: 37.

[5] Lavvas P. P. Planet. Space Sci., 2008, 56: 27.

[6] Lebonnois S. Planet Space Sci., 2005, 53: 486.

[7] Wilson E. H., Atreya S. K. J. Geophys. Res., 2004, 109: E06002.

[8] Vuitton V., Yelle R. V., Cui J. J. Geophys. Res., 2008, 113: E05007.

[9] Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A. Jr., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A. Gaussian 03, Revision B. 03, 2004, Wallingford CT: Gaussian Inc.

[10] Glendening E. D., Badenhoop J. K., Reed A. E., Carpenter J. E., Bohmann J. A., Morales C. M., Weinhold F. NBO 5.0, 2001, Madison WI: Theoretical Chemistry Institute of University of Wisconsin.

[11] Becke A. D. J. Chem. Phys., 1993, 98: 5648.

[12] McLean A. D., Chandler G. S. J. Chem. Phys., 1980, 72: 5639.

[13] Krishnan R., Binkley J. S., Seeger R., Pople J. A. J. Chem. Phys., 1980, 72: 650.

[14] Frisch M. J., Pople J. A., Binkley J. S. J. Chem. Phys., 1984, 80: 3265.

[15] Gonzalez C., Schlegel H. B. J. Chem. Phys., 1989, 90: 2154.

[16] Gonzalez C., Schlegel H. B. J. Chem. Phys., 1990, 94: 5523.

[17] Pople J. A., Head-Gordon M., Raghavachari K. J. Chem. Phys., 1987, 87: 5968.

[18] Curtiss L. A., Raghavachari K., Redfern P. C., Rassolov V., Pople J. A. J. Chem. Phys., 1998, 109: 7764.

[19] Boboul A. G., Curtiss L. A., Redfern P. C., Raghavachari K. J. Chem. Phys., 1999, 110: 7650.

[20] Gauss J., Cremer C. Chen. Phys. Lett., 1988, 150: 280.

[21] Salter E. A., Trucks G. W., Bartlett R. J. J. Chem. Phys., 1989, 90: 1752.

[22] Zhou Z. J., Liu H. L., Huang X. R., Sun C. C. Chem. J. Chinese Universities, 2008, 29(8): 1641.

[23] Carrasco N., Dutuit O., Thissen R., Banaszkiewicz M., Pernot P. Planetary and Space Science, 2006, 55: 141.

[24] Callomon J. H., Stoicheff B. P. Can. J. Phys., 1957, 35: 373.